Compounds comprising a thiocarbonyl-sulfanyl group, which can be used for the radical synthesis of-α-perfluoroalkylamines

ABSTRACT

The invention relates to compounds having the general formula (I), the method of preparation thereof and the use thereof in organic radical synthesis. The invention also relates to compounds having the formula (II), the method of preparation thereof and a method for preparing compounds having the formula (VIII).

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is the U.S. national stage of International ApplicationNo. PCT/FR2003/002697, filed Sep. 11, 2003, which claims priority under35 U.S.C. §119 of French Patent Application No. 02/11261, filed Sep. 11,2002, said applications being hereby expressly incorporated by referencein their entireties and relied upon.

The present invention relates to a new family of compounds which areuseful in particular for the radical synthesis ofα-perfluoroalkylamines.

The introduction of fluorine atoms into a specific molecule generallymodifies the chemical properties thereof significantly. In the case of abiologically active compound, the introduction of fluorine atoms can inparticular lead to a modification of the pharmacological profile of themolecule.

Therefore, numerous attempts are currently being made to developpractical methods for producing various classes of fluorine-containingcompounds, in particular α-perfluoroalkylamines and more particularlyα-trifluoromethylamines.

Trifluoromethylamine compounds having an advantageous biologicalactivity thus include, for example, the following compounds:

The majority of the synthesis methods currently developed for producingα-trifluoromethylamines consist in carrying out a reductive amination ofthe corresponding trifluoromethyl ketone compounds. However, theseapproaches generally suppose the use of a given number of steps toproduce the initial trifluoromethyl ketone compounds and have been foundto produce relatively unsatisfactory overall yields owing to the linearnature of the process; on the other hand, this approach is oftenincompatible with a number of functional groups which are sensitive tothe action of the amine or that of the reducers used, or also to thereagents required for the synthesis of the initial trifluoromethylketones.

Another significant method for producing α-trifluoromethylaminecompounds consists in reacting various nucleophiles, for example, of theenolated type, with iminium salts. In this regard, reference can be madein particular to the following publications: (a) Blond, G.; Billard, T.;Langlois, B. J. Org. Chem. 2001, 66, 4826-4830. (b) Takaya; J. H.;Kagoshima, H.; Akiyama, T. Org. Lett. 2000, 2, 1577-1579. (c) Dolbier,W. R.; Xu, Y. J. Org. Chem. 2000, 65, 2134-2137. (d) Dolbier, W. R.; Xu,Y. J. Tetrahedron Lett. 1998, 39, 9151-9154. (d) Fuchigami, T.;Nakagawa, Y.; Nonaka, T. J. Org. Chem. 1987, 52, 5489-5491). However,the formation of an iminium salt at the foot of a group which is aselectroattractive as a trifluoromethyl generally requires relativelystrict conditions.

Surprisingly, inventors have discovered a new method which allowsα-trifluoromethylamine compounds to be produced, and more generallyα-per-/α-poly-fluoroalkyl/fluoroaryl amine compounds, in a direct,flexible and effective manner with satisfactory yields, starting fromα-per-/α-poly-fluoroalkyl/fluoroaryl amine derivatives which comprise athiocarbonylsulphanyl function in the α-position, and which are capableof reacting with olefins.

Compounds Having the Formula I

According to a first feature, the subject-matter of the invention isthus compounds having the general formula (I):

in which:

-   -   X represents a group which donates through a mesomeric effect;    -   Z₁ represents a group selected from:    -   (i) the alkyl, acyl, aryl, aralkyl, alkene or alkyne groups, the        cyclic hydrocarbons or the heterocycles,    -   (ii) an —OR^(a) or —SR^(a) group in which R^(a) is a group        selected from:    -   an alkyl, halogenoalkyl, alkenyl, alkynyl, acyl, aryl,        arylalkyl, arylalkenyl, arylalkynyl group, or a cyclic        hydrocarbon or a heterocycle, or a polymer chain;    -   a —CR^(b)R^(c)PO(OR^(d))(OR^(e)) group in which:        -   R^(b) and R^(c) each represent, independently of each other,            a hydrogen atom, a halogen atom, an alkyl group,            perfluoroalkyl, a cyclic hydrocarbon or a heterocycle, or an            —NO₂, —NCO, CN group, or a group selected from groups of the            type —R^(f), —SO₃R^(f), —OR^(f), —SR^(f), —NR^(f)R^(g),            —COOR^(f), —O₂CR^(f), —CONR^(f)R^(g), —NCOR^(f)R^(g), in            which R^(f) and R^(g) each independently refer to an alkyl,            alkenyl, alkynyl, cycloalkenyl, cycloalkynyl, aryl group            which is optionally condensed to a heterocycle, alkaryl,            arylalkyl, heteroaryl,        -   or R^(b) and R^(c) form, together with the carbon atom to            which they are attached, a C═O or C═S group or a cyclic            hydrocarbon or a heterocycle group; and        -   R^(d) and R^(e) each represent, independently of each other,            a radical which complies with one of the definitions given            above for the group R^(f);        -   or R^(d) and R^(e) together form a hydrocarbon chain which            comprises from 2 to 4 carbon atoms, and which is optionally            interrupted by a group selected from —O—, —S— and —NR^(h)—;            in which R^(h) complies with one of the definitions given            above for the group R^(f);    -   (iii) a group —NR^(i)R^(j), in which:        -   R^(i) and R^(j) represent, independently of each other, a            radical selected from an alkyl, halogenoalkyl, alkenyl,            alkynyl, acyl, ester, aryl, arylalkyl, arylalkenyl,            arylalkynyl group, or a cyclic hydrocarbon or a heterocycle;            or        -   R^(i) and R^(j) together form a hydrocarbon chain which            comprises from 2 to 4 carbon atoms and which is optionally            interrupted by a —O—, —S—, or —NR^(H), or R^(H) group which            complies with one of the definitions given above for the            R^(f) group, the hydrocarbon chain advantageously forming a            5-membered ring with the nitrogen atom to which R^(i) and            R^(j) are attached,    -   Z₄ represents a hydrogen atom, an alkyl or cycloalkyl group, and    -   Rf represents    -   (i) a halogen atom, preferably fluorine;    -   (ii) fluoroalkyl, preferably perfluoroalkyl;    -   (iii) a poly- or per-halogenated aryl radical, comprising at        least one, advantageously two, fluorine atom(s), or    -   (iv) a radical selected from R_(A)—CF₂—, R_(A)—CF₂—CF₂—,        R_(A)—CF₂—CF(CF₃)—, CF₃—C(R_(A))F— and (CF₃)R_(A)—, with R_(A)        selected from an alkyl, acyl, aryl, aralkyl, alkene or alkyne        group, the cyclic hydrocarbons or the heterocycles;        and the salts of compounds of this type.

Advantageously the group X is, or comprises, a metalloid atom whichcarries a lone pair, such as halogens, chalcogens and metalloids of thenitrogen group.

The “chalcogens” refer to the metalloid atoms selected from oxygen,sulphur, selenium and tellurium.

The metalloids of the nitrogen group include in particular nitrogen,phosphorus and arsenic.

This metalloid atom X carries the bond to the remainder of the molecule,that is to say, to the carbon which carries Rf.

X can thus be selected in particular from —NZ₂Z₃, —OZ₅ or Hal, where

-   -   -Z₂ and Z₃ represent, independently of each other, a hydrogen        atom, a group selected from the alkyls, cycloalkyls, aryls and        the electroattractive groups, it being understood that at least        one of the radicals Z₂ and Z₃ advantageously has an        electroattractive effect with respect to the electron density of        the nitrogen atom to which they are bonded,    -   Z₅ represents a hydrogen atom, an alkyl, cycloalkyl, aryl group,        or a group which is electroattractive with respect to the oxygen        atom to which it is bonded.

X preferably represents —NZ₂Z₃.

When the metalloid atom is divalent (in the case of chalcogens) orpolyvalent (in the case of nitrogen), the availability of the lone paircan be modulated by the substituents. It is thus preferable for asubstituent of the metalloids to be electroattractive. For example, whenX represents an atom of nitrogen or oxygen, the electroattractive groupallows the conjugation of the lone pair of nitrogen or oxygen to bereduced with the thiocarbonylsulphanyl function in the α-position.

For more information on this subject, reference can be made inparticular to the work of Professor Jerry March entitled “AdvancedOrganic Chemistry” (3rd edition), published by John Wiley and Sons.

In the context of the present description, an “electroattractive group”refers to a group which is generally at least as electroattractive asthe phenyl group, and which, in the Hammett constant scale σ_(p),corresponds to the value 0.05; it should be noted that the hydrogenvalue is by definition zero and that of trifluoromethyl is 0.53.According to the present invention, the electroattractive nature of thesubstituent(s) of the metalloid is ensured by the presence of one, andin the case of polyvalent metalloids, preferably only one, carbonylgroup which is directly bonded to the metalloid.

Examples of an electroattractive group include in particular the acylgroups (σ_(p)˜0.47) in the widest possible sense, including aroyl,carboxyl (σ_(p)˜0.44), alkyloxycarbonyl (σ_(p)˜0.44), aryloxycarbonyl,aralkyloxycarbonyl, carbamoyl, alkylcarbamoyl, arylcarbamoyl, the cyano-(σ_(p)˜0.70), sulphonyl, alkylsulphonyl (σ_(p)˜0.73), arylsulphonylgroups, preferably acyl, carboxyl, alkyloxycarbonyl, aryloxycarbonyl,aralkyloxycarbonyl, carbamoyl, cyano-, sulphonyl.

It should be noted that the sigma values p(ara), ((σ_(p))) indicatedabove are those reported in the work of Professor Jerry March entitled“Advanced Organic Chemistry” (3rd edition), published by John Wiley andSons.

The groups Z₂ and Z₃ can also be bonded to form, with the nitrogen atomto which they are bonded, a hydrocarbon, saturated, unsaturated oraromatic heterocycle, which preferably comprises from 5 to 6 chainlinks, and which is optionally interrupted by one or two atoms ofnitrogen.

Preferred examples of heterocycles include in particular azoles, inparticular diazoles, such as imidazole or pyrazole, and triazoles. Whenthe heterocycle is saturated or partially saturated, it may comprisesubstituents of the type oxo (O═) or thioxo (S═). Pyrrolidone can bementioned as a particular example.

In the whole of the present description, the term “alkyl” or “Alk” groupis understood to cover a saturated hydrocarbon radical which is linearor branched and which can optionally include one or more saturatedaliphatic ring(s). In the context of the invention, the alkyl groups mayhave up to 25 carbon atoms and they preferably contain from 1 to 12carbon atoms, and advantageously from 1 to 6 carbon atoms.

The alkyl radicals which can be envisaged include, in particular themethyl, ethyl, propyl, butyl, pentyl, isopropyl, tert-butyl,(cyclo)pentyl, (cyclo)hexyl, octyl, decyl or dodecyl radical.

In the context of the present description, an alkyl group may alsoparticulary refer to a cycloalkyl group, that is to say, a saturatedcyclic hydrocarbon radical which preferably has from 3 to 10 carbonatoms.

In the context of the present description, a “polymer chain” mayoriginate from a radical or ionic polymerisation or a polycondensation.

In the context of the present description, an “alkoxy” group itselfrefers to a radical —OAlk, in which Alk refers to an alkyl group asdefined above.

In the context of the present description, the “halogenoalkyl” group isunderstood to be an alkyl radical as defined above and substituted by atleast one halogen atom, the term “halogen atom” referring in thisinstance, as in the whole description, to an atom of fluorine, chlorine,bromine or iodine, preferably an atom of fluorine or chlorine, andadvantageously an atom of fluorine. The “halogenoalkyl” groups of theinvention can thus be, for example, “perfluoroalkyl” groups, that is tosay, in the context of the invention, groups which comply with theformula C_(n)F_(2n+1), in which n represents a whole number in the orderof from 1 to 20.

Furthermore, an “alkenyl” group, in the sense in which it is used in thepresent description, refers to an unsaturated linear or branchedhydrocarbon radical having at least one double bond C═C. The alkenylgroups of the invention may have from 2 to 25 carbon atoms andpreferably comprise from 2 to 12 carbon atoms, and advantageously from 2to 6 carbon atoms.

Examples of alkenyl groups include in particular ethenyl, propenyl,n-butenyl, i-butenyl and allyl.

In the same manner, “alkynyl” group is understood to be an unsaturatedlinear or branched hydrocarbon radical having at least one triple bondC═C. The alkynyl groups of the invention generally have from 2 to 25carbon atoms, and they preferably comprise from 2 to 15 carbon atoms,and advantageously from 2 to 6 carbon atoms.

In the context of the present description, an “aryl” or “Ar” groupitself refers to an aromatic mono- or polycyclical group generallyhaving from 5 to 20 carbon atoms, and preferably from 6 to 10 carbonatoms. It can thus be, for example, a phenyl or 1- or 2-naphthyl group.According to a specific variant, an “aryl” group in the context of theinvention may include one or more heteroatoms, such as sulphur, oxygen,or nitrogen. In this particular case, the “aryl” group refers to aheteroaromatic mono- or polycyclical group. The “arylalkyl”, “aralkenyl”and “aralkynyl” groups in the context of the present description arealkyl, alkenyl and alkynyl chains substituted by an aryl group asdefined above, respectively.

In the context of the present description, an “acyl” group itself refersto a group having the formula —C(═O)—B, in which B refers to a hydrogenatom or a linear or branched hydrocarbon chain which is saturated orunsaturated and which comprises from 1 to 25 carbon atoms, and which canin particular be an alkyl, alkenyl, alkynyl group, the alkenyl groupbeing able in particular to be an aryl group, as defined above.

“Aroyl” refers to an aryl-CO— group, in which the aryl group is asdescribed in the present document. Examples of types of aroyl groupsinclude benzoyl, 1- and 2-naphthoyl.

Preferred acyl groups are the alkyl-CO— groups in which the alkyl groupmore preferably refers to an alkyl in C₁-C₆. Examples of acyl groupsinclude in particular the formyl, acetyl, propanoyl and pivaloyl groups.

When the acyl groups must also act as a protective group which can bereadily released, the acyls are advantageously ester groups of carbonicacid (—CO—O—B), such as the terbutyloxycarbonyl and benzyloxycarbonylgroups.

In the context of the present description, “ester” group is understoodto be a —C(═O)—OB group, in which B refers to a linear or branchedhydrocarbon chain which is saturated or unsaturated and which comprisesfrom 1 to 25 carbon atoms, and which can in particular be an alkyl,alkenyl or alkynyl group as defined above. The ester groups include inparticular the alkyloxycarbonyl, aryloxycarbonyl and aralkyloxycarbonylgroups.

“Alkyloxycarbonyl” or “alkoxycarbonyl” preferably refer to analkyl-O—OC— group, in which the alkyl group is as defined in the presentdescription. Examples of types of alkoxycarbonyl groups includemethoxycarbonyl, ethoxycarbonyl or t-butoxycarbonyl (Boc).

“Aryloxycarbonyl” preferably refers to an aryl-O—CO— group, in which thearyl group is as defined in the present description. Examples thereofare in particular phenoxycarbonyl and naphthoxycarbonyl.

“Aralkyloxycarbonyl” preferably refers to an aralkyl-O—CO— group, inwhich the aralkyl group is as defined in the present description.Examples of an aralkoxycarbonyl group include in particularbenzyloxycarbonyl.

In the context of the present description, a radical of the “cyclichydrocarbon” type refers to a saturated, unsaturated or aromaticcyclical group, in particular of the cycloalkyl, cycloalkenyl orcycloalkynyl type, optionally substituted, and comprising from 3 to 20carbon atoms. A radical of the “heterocycle” type itself refers to acarbon cycle of this type interrupted by at least one heteroatomselected, for example, from N, O, S, P and Si, the carbon cycle beingable to be saturated or unsaturated.

“Carbamoyl” preferably refers to an NH₂—CO— group.

“Carboxyl” preferably refers to a group HO(O)C— (carboxylic acid).

“Alkylcarbamoyl” preferably refers to an alkyl-NH—CO group, in which thealkyl group is as defined in the present description.

“Sulphonyl” preferably refers to a —SO₃H group.

“Alkylsulphonyl” preferably refers to a group alkyl-SO₂— in which thealkyl group is as defined in the present description.

“Arylsulphonyl” preferably refers to a group aryl-SO₂—, in which thearyl group is as defined in the present description.

The various radicals may optionally be interrupted by one or moreheteroatoms selected in particular from O, S, N, P and Si, or by—(C═O)—, —(C═S)—, —SO₂—, —SO— groups, or secondary or tertiary amines,and they can be substituted by any type of group which is not capable ofinterfering with a radical addition reaction or leading to parasitereactions between the compounds present, and in particular by one ormore identical or different groups selected from the groupsalkoxycarbonyl or aryloxycarbonyl (—COOR), carboxy (—COOH), acyloxy(—O₂CR), carbamoyl (—CONR₂), cyano (—CN), alkylcarbonyl,alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido,maleimido, succinimido, amidino, guanidino, hydroxy (—OH), amino (—NR₂)or (—NH₂), halogen, perfluoroalkyl (C_(n)F_(2n+1)), allyl, epoxy, alkoxy(—OR), thioalkoxy or thioaryloxy (—SR), sulphones, phosphonates, a silylgroup, a halogen atom, groups having hydrophilic or ionic properties,such as the alkaline salts of carboxylic acids, the alkaline salts ofsulphonic acids or phosphonic acids, polyoxide chains of alkylene, suchas polyoxyethylene POE and polyoxypropylene POP, cationic substituents(quaternary ammonium salts), R representing an alkyl or aryl group, or apolymer chain, the substituents optionally being able to be interruptedby heteroatoms. A person skilled in art will be able to select thenature of the various groups and substituents present in the compoundsused in order to prevent any undesirable secondary reaction.

According to one variant of the invention, Z₁ represents an alkyl oraryl group.

According to a particularly preferred embodiment, Z₁ represents a group—OR^(a), in which R^(a) is as defined above. In this case, R^(a) ispreferably a group selected from the alkyls, aralkyls or cycloalkyls.Still more preferably, R^(a) represents an alkyl group.

According to an advantageous variant of the invention, Z₄ represents ahydrogen atom.

Advantageously, Rf represents a group comprising a difluoromethylenechain link which carries the bond which ensures the link with theremainder of the molecule, in particular a R_(A)—CF₂— group.

Rf is preferably fluoroalkyl, more preferably perfluoroalkyl, preferablya trifluoromethyl radical.

According to a specific embodiment, Rf is a poly- or per-halogenatedaryl radical comprising at least one fluorine atom, preferably twofluorine atoms.

According to a preferred method of the invention, the compounds havingthe formula (I) are compounds having the formula (Ia) in which Xrepresents a group —NZ₂Z₃.

According to a preferred variant of the invention, at least one of thegroups Z₂ and Z₃ represents an acyl, alkoxycarbonyl oraralkyloxycarbonyl group, preferably acyl, for example, an acetyl,alkoxycarbonyl. Also advantageous as electroattractive groups Z₂, Z₃ aregroups such as t-butoxycarbonyl (Boc), benzyloxycarbonyl, often used toprotect amines since they can be readily removed.

In this context, it is particularly preferable for the other group Z₂ orZ₃ to represent a hydrogen atom or a hydrocarbon remainderadvantageously having at the most 10 carbon atoms, preferably at themost 4. The hydrocarbon remainder is preferably an alkyl or aryl group.

According to another advantageous feature of the invention, thecompounds are compounds having the formula (I), in which X represents—OZ₅, complying with the formula (Ib):

Z₅ preferably represents a hydrogen atom, an acyl or aroyl group, andmore preferably an acetyl or benzoyl group.

According to another preferred method, the compounds are compoundshaving the formula (I) in which X represents Hal, complying with theformula (Ic):

In the context of the present invention, “Hal” refers to a halogen atom.Hal preferably represents an atom of chlorine or bromine, and morepreferably an atom of chlorine.

In particular when Z₁ represents an alkyl, aryl, —SR^(a), or —OR^(a)group, with R^(a) selected from the alkyl, arylalkyl, cycloalkyl groups,

-   -   Z₄ advantageously represents a hydrogen atom,    -   Rf advantageously represents a perfluoroalkyl chain, preferably        a trifluoromethyl,    -   when X=NZ₂Z₃:    -   Z₂ advantageously represents an electroattractive group, such as        the acyl, alkoxycarbonyl or aralkyloxycarbonyl groups,        preferably acyl or alkoxycarbonyl, including in particular        t-butoxycarbonyl or benzyloxycarbonyl,    -   Z₃ advantageously represents either an electroattractive group        which is identical to or different from Z₂, such as the acyl,        alkoxycarbonyl or aralkyloxycarbonyl groups, preferably acyl or        alkoxycarbonyl, including in particular t-butoxycarbonyl and        benzyloxycarbonyl, or a hydrogen atom, an alkyl, cycloalkyl or        aryl group,    -   when X=OZ₅, Z₅ advantageously represents an acyl group, in        particular aroyl, and more preferably an acetyl or benzoyl        group,    -   when X=Hal, X preferably represents a chlorine atom.

Examples of compounds according to the invention include moreparticularly the following compounds:S-[1-(N-acetylamino)-2,2,2-trifluoroethyl]-O-ethyl dithiocarbonate,S-1-benzoylamino-2,2,2-trifluoro-ethyl dithiocarbonic acid O-ethyldiester, S-(1-hydroxy-2,2,2-trifluoro-ethyl) dithiocarbonic acid O-ethylester, S-(1-acetyl-2,2,2-trifluoro-ethyl) dithiocarbonic acid O-ethylester, 1-ethoxythiocarbonylsulphanyl-2,2,2-trifluoro-ethyl benzoic acidester, S-1-chloro-2,2,2-trifluoro-ethyl dithiocarbonic acid O-ethylester.

Method for Preparing Compounds Having the Formula I

The compounds which can be used according to the invention can beprepared by means of the application or adaptation of known methods,which are understood to be those methods which have been used up to thepresent time or described in literature, for example, those described byR. C. Laroche in “Comprehensive Organic Transformations”, VCHPublishers, 1989.

According to a second feature, the subject-matter of the invention is amethod for preparing compourids having the formula (Ia).

This method comprises the following successive steps:

a) a nucleophilic substitution of the alkoxyl function of hemiacetalRf-C(OAlk)(OH) Z₄, (A) by means of the addition of a Z₂Z₃NH derivativein order to produce a compound having the formula Rf-C(NZ₂Z₃)(OH) Z₄, inwhich Alk refers to an alkyl group, and where Rf, Z₂, Z₃ have the abovemeaning;

b) a halogenation of the hydroxyl function of the compound produced whenstep (a) is complete,

c) a substitution of the halogen group introduced in step (b) by aderivative of thiocarbonylsulphanyl (Z₁-C(═S)—S—) in the form of analkali metal salt, MS—(CS)-Z₁, in which Z₁ has the above meaning and Mrefers to an alkali metal.

The method for preparing a compound having the formula (Ia) according tothe invention can be illustrated by the general synthesis diagram below:

in which Z₁, Z₂, Z₃, Z₄, Rf and M have the above-mentioned definitions,Alk referring to an alkyl group and X to a halogen.

Without wishing to be limited to any one theory, these reactions aremade possible by the presence of the Rf group, which advantageously hasan electroattractive effect which advantageously allows the hydrateaminal and hemiacetal forms (A) to be stabilised.

Whatever their precise sructure, the hemiacetals Rf-C(OAlk)(OH)Z₄ (A)and hydrates Rf-C(OH)₂Z₄ which can be used as starting compounds in step(a) are readily accessible. Although some of these compounds arecommercially available, they can also be prepared according to variousmethods of production described in the following publications: (a)Gross, U.; Rüdinger, S. in Organo-Fluorine Compounds; Baasner. B.;Hagemann, H.; Tatlow, J. C., Eds; Houben-Weyl: Methods of OrganicChemistry; Thieme: Stuttgart, 1999; Vol E10a. (b) Banks, R. E.; Smart,B. E.; Tatlow, J. C. Organofluorine Chemistry: Principles and CommercialApplications; Plenum Press: New York, 1994. (c) Hudlicky, M.; Pavlath,A. E. Chemistry of Organic Fluorine Compounds II. A Critical Review; ACSMonograph 187; American Chemical Society: Washington D.C., 1995.

According to a specific embodiment, the amine derivative Z₂Z₃NH used instep (a) is an amide, and is preferably acetamide.

By way of non-limiting illustration of the solvents which are suitablefor step (a) according to the invention, it is possible to mention inparticular dioxane, tetrahydrofuran or dimethyl ether of ethylene glycol(DME).

The halogenation carried out in step (b) of the method preferablycomprises a chlorination. Chlorination agents which allow a hydroxylfunction to be substituted by a chlorine atom in step (b) and which havebeen found to be particularly advantageous according to the inventioninclude thionyl chloride, phosphorus oxychloride, phosphorustrichloride, phosphorus pentachloride and phosgene.

The invention also relates to a method for preparing compounds havingthe formula (Ib). Compounds having the formula (Ib) can be preparedusing any method known to the person skilled in the art.

Compounds having the formula (Ib), in which Z₅ is differerent from H,can in particular be prepared using a method comprising:

-   -   a) the use of a compound (Ib) in which Z₅=H and a compound Z₅-Y        Z₅ is as defined above and Y refers to a leaving group; and        optionally    -   b) the recovery of the product obtained.

“Leaving group” is understood to be a Z₅-Y bond which readily becomesunstable, in particular under the action of a nucleophile. Leavinggroups are well known to the person skilled in the art. For examples ofleaving groups, reference can be made in particular to the work of T. H.Greene and P. G. Wuts, “Protective Groups”, in Organic Chemistry, JohnWiley and Sons, 1991.

Y preferably represents a group —O(C═O)Alk, —O(C═O)Ar, —O(SO₂)Alk,—O(SO₂)Ar, or a halogen atom, such as chlorine or bromine.

Preferred Z₅Y reagents include in particular monocarboxylic acidanhydrides, acyl halides or aroyl halides.

“Monocarboxylic acid anhydride” refers to a group (alkyl-(C═O))₂O or(aryl(C═O))₂O in which alkyl and aryl are as defined in the presentdescription. Preferred examples thereof are in particular aceticanhydride, butyric anhydride and benzoic anhydride.

“Acyl halide” or “aroyl halide” refers to a alkyl-C(═O)-Hal oraryl-C(═O)-Hal group. Examples of acyl halides, including aroyls, are inparticular acetyl chloride and benzyl chloride.

Step a) of this method preferably comprises the use of an acid or abase.

Examples of an acid which is suitable for use in step a) include inparticular mineral acids, such as nitric acid, phosphoric acid,sulphuric acid, hydrochloric acid and sulphonic acids, such asmethanesulphonic acid, ethanesulphonic acid, benzenesulphonic acid andp-toluenesulphonic acid. The acid is preferably used in catalyticproportions. It is generally intended to activate the departure of theleaving group.

Basic examples include in particular pyridines, including picolines andquinoline, amines, advantageously tertiary amines, such as DABCO(diazabicyclooctane), triethylamine and diisopropylethylamine.

According to another feature, the invention also relates to thepreparation of a compound having the formula (Ib) in which Z₅ representsa hydrogen atom, comprising:

a) the use of a compound having the formula (A):

-   -   with an acid and a compound MS—(C═S)-Z₁ in which Z₁ is as        defined above and M refers to an alkali metal and Alk refers to        an alkyl group; and, if necessary,

b) the recovery of the product obtained.

The acids which can be used in this method are those as defined above.

The invention also relates to a method for preparing compounds havingthe formula (Ic) comprising:

a) the use of a compound having the formula (Ib) in which Z₅=H in thepresence of a halogenation agent, and optionally

b) the recovery of the product obtained.

It is possible to use conventional reagents as a halogenation agent.

Examples of a chlorination agent include in particular phosgene,phosphoric reagents, such as phosphorus pentachloride (PCl₅), phosphorustrichloride (PCl₃), phosphorus oxychloride (POCl₃), and sulphurousreagents, such as thionyl chloride (SOCl₂).

Examples of a bromination agent include in particular the brominatedderivatives of phosphorus.

The solvents which may be suitable for carrying out the methods forpreparing the compounds (Ia), (Ib) and (Ic) according to the inventioncan be selected from ketones, alcohols, non-protic polar solvents,halogenated hydrocarbons and aromatics.

Examples of solvents of the ketone type include in particular acetoneand methyl ethyl ketone.

Examples of solvents of the alcohol type include in particular methanol,ethanol and isopropanol.

Examples of non-protic polar solvents include in particularacetonitrile, N,N-dimethylformamide (DMF) and dimethyl sulphoxide(DMSO).

Examples of a halogenated hydrocarbon include in particulardichloromethane and 1,2-dichloroethane.

Examples of an aromatic solvent include in particular benzene, tolueneand chlorobenzenes.

With regard to solvents which are suitable for carrying out step (c) ofthe method for preparing compounds having the formula (Ia), it ispossible more particularly to mention acetone, acetonitrile, ethanol,isopropanol, methanol, methyl ethyl ketone, N,N-dimethylformamide (DMF),and dimethyl sulphoxide (DMSO).

Examples of a solvent which is particularly suitable for the method forpreparing compounds having the formula (Ib) include in particularacetone and dichloromethane.

The derivatives which comprise a thiocarbonylsulphanyl function(Z₁-C(═S)—S—) and which can be used in step (c) include in particularxanthate compounds (Z₁=OR^(a)), dithiocarbamates (Z₁=NR^(b)R^(c)),trithiocarbonates (Z₁=SR^(a)). With regard to the groups R^(a), R^(b),and R^(c), they comply with the definitions set out above.

R^(a), R^(b) and R^(c) preferably represent an alkyl group, preferablyan alkyl in C₁-C₆.

Preferred examples include xanthate derivatives, for example, potassiumO-ethylxanthate.

Compounds having the formula (Ia), (Ib) and (Ic) can be separated andpurified using conventional separation and purification techniques, forexample, by means of filtration, concentration, extraction,crystallisation, recrystallisation, column chromatography or acombination of methods of this type.

Compounds having the formula (I), preferably compounds having theformula (Ia), have been found to be particularly advantageous in thecontext of radical organic synthesis reactions.

Under thermal, chemical or photochemical activation, preferably chemicalor photochemical activation, compounds having the formula (I) result inRfC.(Z₄)(X) radicals.

They are preferably compounds having the formula (Ia) which result inRf-C.(Z₄)(NZ₂Z₃) radicals.

These radicals can then react with unsaturated compounds, such asolefins.

Activation is understood to be a process which allows the production ofa radical Rf-C.(Z₄)(X), preferably Rf-C.(Z₄)(NZ₂Z₃) starting from acompound having the formula (I). This activation can be brought about inparticular by the photons of an actinic source, in particular luminoussource (photochemical activation), by the thermal decomposition of aninitiator of free radicals, for example, a peroxide or a diazo compound(chemical activation), or by the autoxidation of a compound which issensitive to oxygen, such as triethylborane.

Preferred examples of an initiator include peroxides, which arepreferably symmetrical, and azo compounds. The peroxides include alkyl,and in particular tertioalkyl, peroxides, and acyl, in particularalkanoyl, peroxides which are preferably symmetrical.

The acyl peroxides which can be used are preferably peroxides whoseacyls have a low molecular weight, that is to say, their number ofcarbon atoms is at the most equal to 10, preferably 6 when they arealiphatic, but it is preferable to use acyl peroxides of an aromaticnature, such as benzoyl peroxide.

Examples of an initiator of the peroxide type include in particularbenzoyl peroxide, cumene hydroperoxide, hydrogen peroxide, acetylperoxide and lauroyl peroxide.

Examples of initiators of the azo type (azobisnitrile) include inparticular 2,2′-azobis-isobutyronitrile,2,2′-azobis-(2-methyl-propanenitrile),2,2′-azobis-(2,4-dimethylpentanenitrile),2,2′-azobis-(2,4-dimethyl-4-methoxyvaleronitrile),2′,2′-azobis-(2,4-dimethylvalero-nitrile) and2,2′-azobis-(2-amidinopropane) hydrochloride.

In this regard, reference can be made in particular to the work “PolymerHandbook”, 4th edition, ed. D. Bloch.

Use of Compounds Having the Formula (I)

The use of compounds having the formula (I) in radical organic synthesismaking use of this type of method constitutes another feature of theinvention.

More precisely, compounds having the formula (I), including inparticular compounds having the formula (Ia), are particularly useful inradical organic synthesis, as a source of Rf-C.(Z)(X) radicals,including in particular (Rf-C.(Z₄)(NZ₂Z₃)) radicals, which can beactivated photochemically or chemically.

In this context, compounds having the formula (I), respectively (Ia),can be used to introduce an Rf(Z₄)(X)C—, Rf(Z₄)(NZ₂Z₃)C— group,respectively, in particular perfluoroalkylamine, in particular theradical 2,2,2-trifluoroethylamine, to an olefin.

Compounds having the formula (I) are used in particular to introduce oneof the groups, (1a), (1b) or (1c) to an olefin:

and in particular one of the groups (1′a), (1′b) or (1′c):

Method for Preparing Compounds Having the Formula (II)

According to another feature, the subject-matter of the invention isthus a method for preparing compounds having the formula (II):

in which

-   -   X, Z₁ and Z₄ have the above-mentioned definitions,    -   Rf represents        -   (i) a halogen atom, preferably fluorine;        -   (ii) halogenoalkyl, preferably fluoroalkyl, more preferably            a perfluoroalkyl group (C_(n)F_(2n+1));        -   (iii) a poly- or per-halogenated aryl radical, or        -   (iv) a radical selected from R_(A)—CF₂, R_(A)—CF₂—CF₂—,            R_(A)—CF₂—CF(CF₃)—, CF₃—C(R_(A))F— and (CF₃)R_(A)—, with            R_(A) selected from an alkyl, acyl, aryl, aralkyl, alkene or            alkyne group, cyclic hydrocarbons or heterocycles,    -   Z₆, Z₇, Z₈ and Z₉ independently represent a hydrogen atom, a        halogen atom, an alkyl, halogenoalkyl, alkenyl, alkynyl, acyl,        aryl, arylalkyl, arylalkenyl, arylalkynyl group, or a cyclic        hydrocarbon or a heterocycle, a polymer chain, a group        —(CH₂)_(m)—OR^(k), —(CH₂)_(m)—CH(OR^(k))(OR^(l)),        CH(OR^(k))(OR^(l))—, —(CH₂)_(m)—SR^(k), —(CH₂)_(m)—SO₃R^(k),        —(CH₂)_(m)—NO₂, —(CH₂)_(m)—CN, —(CH₂)_(m)—R^(k),        —[(CH₂)_(m)—P(O)(OR^(k))(OR^(l))], (CH₂)_(m)—SiR^(k)R^(l)R^(m),        —(CH₂)_(m)—COOR^(k), —(CH₂)_(m)—NCOR^(k),        —(CH₂)_(m)—NR^(k)R^(l), in which:        -   R^(k), R^(l) and R^(m) each independently refer to an alkyl,            acyl, aryl, alkenyl, alkynyl, aralkyl, alkaryl,            alkylsulphonyl, arylsulphonyl group, a cyclic hydrocarbon or            a heterocycle,        -   or R^(k) and R^(l) together form, with the atom to which            they are attached, a cyclic hydrocarbon or a heterocycle;        -   m referring to a whole number which is greater than or equal            to 1, preferably in the order of from 1 to 100, and            advantageously from 1 to 20, and even more advantageously            from 1 to 4,

or Z₆, Z₇, Z₈ and Z₉ form, two by two, one or more cyclic hydrocarbon(s)or heterocycle(s), the groups Z₆, Z₇, Z₈ and Z₉ which do not form a ringbeing selected from the radicals mentioned above,

the groups alkyl, halogenoalkyl, alkoxy, halogenoalkyl, alkenyl,alkynyl, acyl, ester, carbon cycle, aryl, arylalkyl, alkaryl, aralkenyl,aralkynyl, alkylsulphonyl, arylsulphonyl being as defined above,

the method comprising the reaction of a compound having the formula (I)with at least one olefin having the formula (III):

in which Z₆, Z₇, Z₈ and Z₉ are as defined above, in the presence of asource of free radicals, in an organic solvent which is inert relativeto radicals, and the recovery of the compound having the general formula(II).

X preferably represents —NZ₂Z₃, —OZ₅ or Hal, more preferably NZ₂Z₃, Z₂,Z₃, Z₅, and Hal having the above-mentioned definitions for the compoundshaving the formula (I).

The invention also relates to compounds having the formula (II) whichare capable of being produced according to this method.

The compounds having the formula (II) are preferably compounds in whichX=NZ₂Z₃, having the formula (IIa):

More precisely, the preparation of the compounds having the formula (II)consists in an addition of a radical of a compound having the formula(I) to an olefin having the formula (III).

The olefin having the formula (III) is preferably a monosubstitutedolefin in which one of the groups Z₆, Z₇, Z₈ and Z₉ represents asubstituent different from H, the others being H.

In a particularly advantageous manner, it has been shown that the group—S—C(═S)-Z₁ is generally selectively added to the carbon which carries asubstituent which is different from H of the monosubstituted olefin.

“Selectively” is understood to be a level of selectivity preferablygreater than 80%, more preferably greater than 90%, and even moreadvantageously greater than 95%.

Generally, the olefin used is introduced at the rate of from 1 to 3equivalents relative to the compound having the formula (I).

Examples of cyclic hydrocarbons or heterocycles formed by two of thegroups Z₆, Z₇, Z₈ or Z₉ include in particular the cycloalkyls, such ascyclopropane, or heterocycles, such as 1,3-dioxolane,1,3-dioxolan-4-one.

—(CH₂)_(m)—OR^(k) preferably represents a group —(CH₂)_(m)—OCOAlk,—(CH₂)_(m)—O—CO—Ar, —(CH₂)_(m)—CO-Alk or —(CH₂)_(m)—CO—Ar.

Preferred examples include in particular the groups —O—CO—CH₃,—CH₂—O—(CO)—CH₃, —(CH₂)₂—O—CO—CH₃, —(CH₂)₂—CO—CH₃.

—(CH₂)_(m)—CH(OR^(k))(OR^(l)) preferably refers to a group—(CH₂)_(m)—CH(OAlk₁)(OAlk₂) in which Alk₁ and Alk₂ are alkyl groupswhich are identical or different, as defined above. Examples include inparticular —CH₂—CH(OEt)₂ and —CH(OEt)₂.

—(CH₂)_(m)—P(O)(OR^(k))(OR^(l)) preferably refers to a group—(CH₂)_(m)—P(O)(OAlk₁)(OAlk₂) in which Alk₁ and Alk₂ refer to an alkylgroup as defined above. Examples include in particular —CH₂—P(O)(OEt)₂and —CH₂—P(O)(OMe)₂.

—(CH₂)_(m)—SiR^(k)R^(l)R^(m) preferably refers to a group—(CH₂)_(m)—Si(Alk₁) (Alk₂)(Alk₃) in which Alk₁, Alk₂, Alk₃ refer toalkyl groups which are identical or different, as defined above.Examples include in particular —CH₂—SiMe₃.

—(CH₂)_(m)—NR^(k)R^(l) preferably refers to a group in which R^(k) andR^(l) preferably independently represent a hydrogen atom, an alkyl,aryl, aralkyl, heteroaralkyl, alkylsulphonyl group, or form, with theatom of nitrogen to which they are attached, a heterocycle as definedabove, preferably comprising from 4 to 8 carbon atoms.

When the heterocycle is saturated or partially saturated, it maycomprise substituents of the type oxo (O═) or thioxo (S═).

Examples of a preferred NR^(k)R^(l) group include in particular theN-arylalkylsulphonamide groups, such as N(4-bromo-phenyl)methanesulphonamide.

Examples of a heterocyclical —NR^(k)R^(l) group include in particularthe heterocycles pyrrolidin-2-one, isoindolyl-1,3-dione, phthalimide,aziridinyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, piperidyl andpiperazinyl.

According to one specific embodiment, the olefin having the formula(III) is a compound in which the groups Z₆, Z₇, Z₈ and Z₉ are selectedfrom the following groups:

-   -   hydrogen,    -   —OAc,    -   —CH₂—OAc,    -   —(CH₂)₂—OAc,    -   —CH₂—SiMe₃,    -   —CH₂—CN,    -   —CH(OEt)₂, —CH₂—CH(OEt)₂,    -   —CH₂—P(O)(OEt)₂, —CH₂—P(O)(OMe)₂,    -   —(CH₂)₂—COMe,    -   pyrrolidin-2-one,    -   2-methyl-isoindole-1,3-dione,    -   (4-bromo-phenyl)-dimethylamine,        or Z₆, Z₇, Z₈ and Z₉ together form, two by two, a        1,3-dioxol-2-one cycle,        in which the symbol “Ac” represents an acetyl group, “Et”        represents an ethyl group, and “Me” represents a methyl.

By way of non-limiting example, the olefin having the formula (III)which is used can be selected from the following compounds: vinylacetate, hex-5-en-2-one, allyl acetate, vinyltrimethylsilane,but-3-enenitrile, 3,3-diethoxypropene, diethyl allylphosphonate.

The source of free radicals refers, in the context of the presentdescription, to a source which is capable of activating compounds havingthe formula (I), and therefore bringing about the radical reaction. Thecompounds may be subjected to activation of a photo-chemical nature, inparticular by means of exposure to light, or chemical nature, forexample, by means of decomposition of a peroxide.

The activation preferably results from the decomposition of a chemicalinitiator, such as a peroxide or a diazo compound (thermaldecomposition), or decomposition, by means of autoxidation with oxygen,of an organometallic compound, such as triethylborane, diethylzinc,trialkylaluminium.

Examples of peroxides which are particularly suitable as a source offree radicals in the method of the invention, thus include in particulardiisobutyryl peroxide, cumyl peroxyneodecanoate, ter-amylperoxyneodecanoate, di(2-ethylhexyl) peroxydicarbonate, tert-butylperoxyneodecanoate, dibutyl peroxydicarbonate, dicetylperoxydicarbonate, dimyristyl peroxydicarbonate, tert-butylperoxyneoheptanoate, tert-amyl peroxypivalate, didecanoyl peroxide,tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate,1,4-di(tert-butylperoxycarbo)cyclohexane, tert-butyl peroxyacetate,tert-butyl peroxybenzoate, di-tert-amyl peroxide, tert-butyl cumylperoxide, bis-tertiobutyl peroxide, dicumyl peroxide, dilauroyl peroxideor di(4-tert-butylcyclohexyl)peroxydicarbonate.

Regardless of its precise nature, the source of free radicals usedaccording to the method of the invention is used in conditions whichallow the production of free radicals, which is generally brought aboutby means of thermal activation, that is to say, by raising thetemperature of the reaction medium which is generally at a temperaturein the order of ambient temperature (approximately 20° C.) to 200° C.,preferably from 40° C. to 180° C., advantageously from 80° C. to 160° C.The production of free radicals can also be carried out at a lowtemperature, generally at a temperature lower than ambient temperature,preferably from 10° C. to −78° C., by using free radical sources whichare sensitive to the process of autoxidation with oxygen. Generally, theselection of the source of free radicals depends on the temperature atwhich it is desirable to carry out the reaction.

The quantity of the source of free radicals to be introduced into themedium is dependent on a number of parameters, including in particularthe efficiency thereof, the method of introduction, the purity of thereagents, the concentration of the reaction medium, the efficiency ofthe olefin as a radical trap. The person skilled in the art would becapable of adjusting the quantity of the source of free radicals to beintroduced into the medium in accordance with these various parameters.Generally, the source of free radicals used is introduced in a quantitysuch that the quantity of free radicals which it is capable of releasingis between 50% and 200% in moles, and preferably between 2% and 30% inmoles, relative to the total molar quantity of thiocarbonylsulphanylfunctions carried by the compounds having the formula (I) present in themedium.

The solvent used in the method for preparing compounds having theformula (II) is selected from the solvents conventionally used inradical synthesis, such as 1,2-dichloroethane, dichloromethane, benzene,toluene, trifluoromethylbenzene (trifluorotoluene), chlorobenzene,hexane, cyclohexane, heptane, octane, ethyl acetate, tert-butyl alcohol.

The reaction is generally carried out under atmospheric pressure, at theebullition temperature of the selected solvent.

Compounds Having the Formula (II)

Compounds having the formula (II) produced by the method defined aboveare novel and also constitute subject-matter of the present invention.

Compounds having the formula (II) include in particular:

-   -   ester of        S-[1-(2-acetylamino-3,3,3-trifluoro-propyl)-4-oxo-pentyl]        dithiocarbonic acid O-ethyl ester,    -   ester of        S-[5-(1-acetylamino-2,2,2-trifluoro-ethyl)-2-oxo-[1,3]dioxolan-4-yl]        dithiocarbonic acid O-ethyl ester,    -   ester of        3-acetylamino-1-ethoxythiocarbonylsulphanyl-4,4,4-trifluoro-butyl        acetic acid,    -   ester of        S-(3-acetylamino-4,4,4-trifluoro-1-trimethyl-silanylmethyl-butyl)        dithiocarbonic acid O-ethyl ester,    -   ester of S-(3-acetylamino-1-cyanomethyl-4,4,4-trifluoro-butyl)        dithiocarbonic acid O-ethyl ester,    -   ester of        S-(3-acetylamino-1-diethoxymethyl-4,4,4-trifluoro-butyl)        dithiocarbonic acid O-ethyl ester,    -   ester of        S-[3-acetylamino-1-(1,3-dioxo-1,3-dihydro-isoindol-2-ylmethyl)-4,4,4-trifluoro-butyl]        dithiocarbonic acid O-ethyl ester,    -   ester of        (4-acetylamino-2-ethoxythiocarbonylsulphanyl-5,5,5-trifluoro-pentyl)        diethyl phosphonic acid,    -   ester of        4-acetylamino-2-ethoxythiocarbonylsulphanyl-5,5,5-trifluoro-pentyl        acetic acid,    -   ester of        S-[3-acetylamino-4,4,4-trifluoro-1-(2-oxo-pyrrolidin-1yl)-butyl]        dithiocarbonic acid O-ethyl ester,    -   ester of        S-[3-acetylamino-1-{[(4-bromophenyl)-methane-sulphonyl-amino]-methyl}-4,4,4-trifluoro-butyl)        dithiocarbonic acid O-ethyl ester,    -   ester of        S-[1-(2-acetylamino-3,3,3-trifluoro-propyl)-2-phenyl-cyclopropane]        dithiocarbonic acid O-ethyl,    -   ester of        4-benzoylamino-2-ethoxythio-carbonyl-sulphanyl-5,5,5-trifluoro-butyl        acetic acid,    -   4-tertbutyloxycarbamate-2-ethoxythiocarbonyl-sulphanyl-5,5,5-trifluoro-pentyl        ester of acetic acid,    -   O-ethyl and        S-(3-tertbutyl-oxycarbamate-1-diethoxy-methyl-4,4,4-trifluoro-pentyl)        diester of dithiocarbonic acid,    -   O-ethyl and        S-[3-acetoxy-1-(1,3-dioxo-1,3-dihydro-isoindol-2-ylmethyl)-4,4,4-trifluoro-butyl]        diester of dithiocarbonic acid,    -   O-ethyl and        S-[3-acetoxy-4,4,4-trifluoro-1-trimethyl-silanylmethyl-butyl]        diester of dithiocarbonic acid,    -   3-acetoxy-1-ethoxythiocarbonylsulphanyl-4,4,4-trifluoro-butyl        ester of acetic acid,    -   O-ethyl and        S-(3-acetoxy-1-diethoxymethyl-4,4,4-trifluoro-pentyl) diester of        dithiocarbonic acid,    -   O-ethyl and S-(3-acetoxy-1-cyanomethyl-4,4,4-trifluoro)butyl        ester of dithiocarbonic acid,    -   O-ethyl and S-1-(2-acetoxy-3,3,3-trifluoro-propyl)-4-oxo-pentyl        diester of dithiocarbonic acid,    -   4-[4-bromo-phenyl)-methanesulphonyl-amino]-3-ethoxy-carbonylsulphanyl-1-trifluoromethyl-butyl        ester of acetic acid,    -   O-ethyl and        S-3-chloro-4,4,4-trifluoro-1-trimethylsilanylmethylbutyl diester        of dithiocarbonic acid,    -   4-chloro-2-ethoxythiocarbonylsulphanyl-5,5,5-trifluoro-pentyl        ester of acetic acid,    -   O-ethyl and        S-3-chloro-1-(1,3-dioxo-1,3-dihydro-isoindol-2-ylmethyl)-4,4,4-trifluoro-butyl        ester of dithiocarbonic acid,    -   O-ethyl and S-1-(2-chloro-3,3,3-trifluoro-propyl)-4-oxo-pentyl        diester of dithiocarbonic acid,    -   dimethyl and        4-chloro-2-ethoxythiocarbonyl-sulphanyl-5,5,5-trifluoro-pentyl        ester of phosphonic acid,    -   O-ethyl and S-3-chloro-1-cyanomethyl-4,4,4-trifluoro-butyl        diester of diester of dithiocarbonic acid,    -   O-ethyl and S-3-chloro-1-diethoxymethyl-4,4,4-trifluoro-pentyl        dithiocarbonic acid,    -   O-ethyl and        S-3-chloro-1-(4-chloro-phenoxymethyl)-4,4,4-trifluoro-butyl        diester of dithiocarbonic acid,    -   O-ethyl and        S-3-chloro-4,4,4-trifluoro-1-(2-oxo-pyrrolidin-1-yl)-butyl        diester of dithiocarbonic acid.

Compounds having the formula (II) are particularly advantageous,particularly as an intermediate for organic synthesis, in particular inradical chemistry. In the same manner as the compounds having theformula (I), these compounds surprisingly have a high degree ofreactivity, in particular in radical chemistry, in particular withrespect to olefins and most particularly with respect to monosubstitutedolefins.

Compounds having the formula (II) thus constitute key intermediates forthe organic synthesis of functionalised compounds, such asα-perfluoroalkylamine derivatives, α-perfluoroalcohols or the halides ofα-perfluoroalkyls, which are generally difficult to produce.

Methods for Converting Compounds Having the Formula (II)

The method for converting compounds having the formula (II) alsoconstitutes subject-matter of the present invention.

In this case, the method according to the invention comprises the use ofa compound having the formula (II) in one of the following reactions:

-   -   reduction,    -   removal,    -   addition to an olefin,    -   oxidation of the carbon which carries the thiocarbonylsulphanyl        function in aldehyde,        wherein these reactions result in the conversion or the        displacement of the thiocarbonylsulphanyl function.

In the context of the present description, a “reduction” reaction isunderstood to be any reaction which involves the supply of electrons, bymeans of a reductive reagent which is rich in electrons, to thethiocarbonylsulphanyl function of the compound having the formula (II).This reaction results in the substitution of the thiocarbonylsulphanylfunction by a hydrogen atom as illustrated in the general formula (IV):

in which the groups Rf, X, Z₄, Z₆, Z₇, Z₈ and Z₉ have the above meaningfor the compounds having the formula (II).

Compounds having the formula (IV) are particularly preferred, in whichX=—NZ₂Z₃ where Z₂ and Z₃ have the above meaning.

The “removal” reaction, in the sense in which it is used in the presentdescription, refers to a reaction resulting from two consecutive orconcerted departures of two entities of a different nature, that is tosay, a proton H⁺ brought about by the attack of a base, on the one hand,and the departure of the anion ⁻S(CS)Z₁ brought about by the adjacentcarbanion (in the α-position). This reaction leads to the production ofa product which comprises a double bond between the carbon whichinitially carries the thiocarbonylsulphanyl function and the carbon inthe α-position, complying with the general formula (V):

The method for preparing compounds having the formula (IV) according tothe invention therefore comprises the use of a compound having theformula (II) in which the groups X, Z₄, Z₆, Z₇, Z₈ and Z₉ and Rf havethe above meaning, it being understood that at least one of the groupsZ₆ and Z₈ represents a hydrogen atom, with a base.

Examples of a base include in particular tetrabutylammonium fluoride.

X preferably represents NZ₂Z₃ where Z₂ and Z₃ have the above meaning.

A “radical addition” reaction of a compound (II) to an olefinZ₁₀Z₁₁(C═C)Z₁₂Z₁₃, in the presence of a source of free radicals,complying with the definitions set out above, leads to the production ofa compound which complies with the general formula (VI):

In which Rf, X, Z₄, Z₆, Z₇, Z₈ and Z₉ are as defined above and Z₁₀, Z₁₁,Z₁₂ and Z₁₃ comply with the definitions given above for Z₆, Z₇, Z₈ andZ₉.

“Oxidation of the carbon which carries the thiocarbonylsulphanylfunction in aldehyde” is understood to be any reaction, in the presenceof an organic or mineral acid, of a compound having the formula (II) inwhich Z₇, Z₉ each represent an acyloxy- radical and a hydrogen atom,resulting in compounds having the general formula (VII):

in which Rf, X, Z₄, Z₆ and Z₈ are as defined above.

X preferably represents —NZ₂Z₃ where Z₂ and Z₃ have the above meaning.

The aldehyde (VII) produced in the form of an acetal is also includedwithin the concept of the invention.

By way of illustration of compounds produced using one of the methodsfor converting the above compounds having the formula (II), it ispossible to mention in particular:

-   -   N-[3-(2-oxo-pyrrolidin-1-yl)-1-trifluoromethyl-allyl] acetamide,    -   N-[4-(1,3-dioxo-1,3-dihydro-isoindol-2-yl)-1-trifluoromethyl-butyl]        acetamide,    -   ester of        S-{1-[5-(1-acetylamino-2,2,2-trifluoro-ethyl)-2-oxo-[1,3]dioxolan-4-ylmethyl]-2,2-diethoxy-ethyl}        dithiocarbonic acid O-ethyl ester,    -   N-[1-(5-bromo-1-methanesulphonyl-2,3-dihydro-1H-indol-3-ylmethyl)-2,2,2-trifluoro-ethyl]-acetamide,    -   N-(3,3-dimethoxy-1-trifluoromethyl-propyl)-acetamide,    -   4-acetyl-5,5,5-trifluoro-pent-1-ene,    -   ester of        1-[5-bromo-1-methanesulphonyl-2,3-dihydro-1H-indol-3-ylmethyl)-2,2,2-trifluoro-ethyl]        acetic acid,    -   1-(3-chloro-4,4,4-trifluoro-but-1-enyl)-pyrrolidin-2-one,    -   2-(4-chloro-5,5,5-trifluoro-pentyl)-isoindole-1,3-dione.        Method for Preparing Compounds Having the Formula (VIII)

Following photochemical or chemical activation in the absence ofreactive compounds, compounds having the formula (I) may lead to theformation of a compound having the general formula (VIII):

in which X and Z₄ are as defined above,

-   and Rf represents:    -   (i) a fluorine atom;    -   (ii) fluoroalkyl, more preferably perfluoroalkyl;    -   (iii) a poly- or per-halogenated aryl radical, or    -   (iv) a radical selected from R_(A)—CF₂, R_(A)—CF₂—CF₂—,        R_(A)—CF₂—CF(CF₃)—, CF₃—C(R_(A))F— and (CF₃)R_(A)—, with R_(A)        selected from an alkyl, acyl, aryl, aralkyl, alkene or alkyne        group, cyclic hydrocarbons or heterocycles.

X preferably represents —NZ₂Z₃ or —OZ₅, more preferably —NZ₂Z₃, Z₂, Z₃and Z₅ being as defined previously.

By way of illustration of preferred compounds having the formula (VIII),it is possible to mention in particular an ester of2-benzoxy-3,3,3-trifluoro-1-trifluoromethyl-propyl benzoic acid andN-(2-acetylamino-3,3,3-trifluoro-methylpropyl)acetamide.

The method for preparing compounds of this type having the formula(VIII) constitutes, according to another feature, subject-matter of theinvention.

More precisely, the method according to the invention comprises a stepfor radical dimerisation of a compound having the general formula (I)and a step for recovering the compound having the formula (VIII).

In the context of the present invention, radical dimerisation isunderstood to be the formation of a carbon-carbon bond between twoidentical (X) (Rf)(Z₄)C. radicals.

This reaction comprises the use of a compound having the formula (I),preferably (Ia) or (Ib), with a source of free radicals.

In this context, it is particularly preferable for at least one of thegroups Z₂ and Z₃ to represent an acyl group.

Z₅ preferably represents an acyl group, including aroyl, more preferablya benzoyl group.

With regard to the temperature and pressure conditions as well as thenature of the solvent and the source of free radicals which areparticularly suitable for the radical dimerisation method according tothe invention, they comply with the definitions set out above for themethod for preparing compounds having the formula (II).

The compound (VIII) is generally produced in this context by means ofdimerisation of the radical originating from the compound (I) withitself, in the presence of an at least stoichiometric quantity of asource of free radicals.

As has been emphasised above, one advantage of the compounds (I)according to the invention is that they have a high degree of reactivityin radical synthesis, in particular with respect to olefins.

These compounds have been found to be particularly advantageous in thiscontext for introducing an (X)(Rf)(Z₄)C— group, in particular to a largevariety of functional or non-functional olefins.

Another advantage is that the method for preparing compounds having theformula (II) constitutes a particularly flexible method for producingα-perfluoroalkylamine derivatives. The thiocarbonylsulphanyl function(Z₁-C(═S)—S—) present on the compound (II) can be readily reduced,removed, or even bring about a plurality of consecutive radicalreactions. The resultant products can thus represent a particularlyadvantageous network for leading to complex trifluoromethylatedstructures.

Generally, the base products and reagents used in the methods forpreparing compounds having the formula (I), (II) and (VIII) areinexpensive.

Furthermore, the method for preparing compounds having the formula (II)according to the invention advantageously requires neutral experimentalconditions and is therefore compatible with a large number of chemicalfunctions which can be present on the olefin partner.

In a particularly advantageous manner, compounds having the formula (II)in the context of the invention provide convergent and rapid access toprocessed structures which contain a great variety of functions.

Finally, the presence of the thiocarbonylsulphanyl group, in particulara xanthate group, on the formed product (II) advantageously providesaccess to the extremely rich chemistry of sulphur (via thiols,sulphides, sulphones, sulphonic acids, sulphonamides, sulphonium salts,the ylides of sulphur, etc . . . ).

The following examples are given by way of non-limiting illustration ofthe present invention.

EXAMPLES Example of Method for Preparing Compounds Having the Formula(IA) Example 1 Preparation ofS-[1-(N-acetylamino)-2,2,2-trifluoroethyl]-O-ethyl dithiocarbonate

a) N-(2,2,2-trifluoro-1-hydroxy-ethyl)-acetamide

C₄H₆F₃NO₂ M=157.09 g.mol⁻¹Reaction:

A solution of 2,2,2-trifluoro-1-methoxy-ethanol (6.50 g, 50 mmol) andacetamide (2.95 g, 50 mmol) in 75 ml of 1,4-dioxane is brought to refluxfor one hour. After returning to ambient temperature, the reactionadmixture is concentrated at reduced pressure before being purified.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 4/6).

Product:

White crystalline.

Yield:

65%

MP (° C.)

117-119 (ethyl acetate-heptane)

b) N-(1-chloro-2,2,2-trifluoro-ethyl)-acetamide

C₄H₅ClF₃NO M=175.54 g.mol⁻¹Reaction:

A solution of alcohol a (2.00 g, 12.73 mmol) and phosphoruspentachloride (3.05 g, 14.64 mmol) is agitated at ambient temperaturefor 30 minutes, then at 70° C. for 15 minutes. After evaporation atreduced pressure, the residue is purified.

Purification:

Crystallisation.

Product:

White crystalline.

Yield:

59%

MP (° C.)

78-81 (petroleum ether)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 2.14 (s, 3H, COCH₃); 6.34 (qd, J=5.3 Hz,11.1 Hz, 1H, CF₃CH); 6.47 (d, J=10.0 Hz, 1H, NH).

IR (ν, cm⁻¹)(CCl₄) 3436 (NH); 3315 (NH); 2995; 1726 (C═O); 1497; 1370;1345; 1282; 1253; 1221; 1203; 1140.

c) Ester of dithiocarbonic acid S-(1-acetylamino-2,2,2-trifluoro-ethyl)O-ethyl ester

C₇H₁₀F₃NO₂S₂ M=261.29 g.mol⁻¹Reaction:

The salt of potassium ethylxanthogenate (208 mg, 1.29 mmol) is added toa solution of the chlorinated compound b (208 mg, 1.18 mmol) in 5 ml ofacetone. After 15 minutes at ambient temperature, the reaction admixtureis concentrated at reduced pressure. The residue is placed in ether,filtered and concentrated once more at reduced pressure.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 2/8).

Product:

White crystalline.

Yield:

100%

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.44 (t, J=7.0 Hz, 3H, CH₂CH₃); 2.09 (s,3H, COCH₃); 4.69 (q, J=7.0 Hz, 2H, CH₃CH₂); 6.59 (qd, J=7.6 Hz, 10.0 Hz,1H, CF₃CH); 6.89 (d, J=10.0 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.68 (CH₃CH₂); 22.96 (CH₃CO); 57.83(q, J=38 Hz, CF₃CH); 71.42 (CH₂CH₃); 123.48 (q, J=280 Hz, CF₃); 169.63(C═O); 206.87 (C═S).

IR (ν, cm⁻¹)(CCl₄) 3441 (NH); 2983; 1714 (C═O); 1489; 1368; 1331; 1270;1234; 1196; 1122; 1047.

MP (° C.)

84-86 (ethyl acetate-heptane)

Mass (IC, NH₃)

262 (MH⁺), 279 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 32.18 3.86 Actual(found)(%) 32.57 3.91

Example 2 Preparation of O-ethyl andS-1-tert-butyloxycarbonyl-amino-2,2,2-trifluoro-ethyl diester ofdithiocarbonic acid

a) N-(2,2,2-trifluoro-1-hydroxy-ethyl)tert-butylcarbamate

C₇H₁₂F₃NO₃ M=215.17 g.mol⁻¹Reaction:

A solution of 2,2,2-trifluoro-1-methoxy-ethanol (1.63 g, 12.5 mmol) andtert-butylcarbamate (1.46 g, 12.5 mmol) in 1,4-dioxane (20 ml) isbrought to reflux for one hour. After returning to ambient temperature,the reaction admixture is concentrated at reduced pressure before beingpurified.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 4/6).

Product:

White crystals.

Yield:

55%.

MP

118° C. (ethyl acetate-heptane)

b) N-(1-chloro-2,2,2-trifluoro-ethyl)-tert-butylcarbamate

C₇H₁₁ClF₃NO₂ M=233.04 g.mol⁻¹Reaction:

Thionyl chloride (85 μL, 1.16 mmol) and pyridine (95 μL, 1.4 mmol) areadded to a solution of alcohol A8 (250 mg, 1.16 mmol) in dichloromethane(10 ml). After 1.5 hours under reflux, the reaction admixture is cooledand concentrated at reduced pressure.

Product:

Yellow crystals.

Yield:

61%

MP

125° C. (ethyl acetate-heptane)

c) O-ethyl S-1-tert-butyloxycarbonylamino-2,2,2-trifluoro-ethyl diesterof dithiocarbonic acid

C₁₀H₁₆F₃NO₃S₂ M=319.05 g.mol⁻¹Reaction:

The salt of potassium ethylxanthogenate (230 mg, 1.42 mmol) is added toa solution of the chlorinated compound A10 (165 mg, 0.71 mmol) inacetone (8 ml). After 30 min at ambient temperature, the reactionadmixture is concentrated at reduced pressure. The residue is placed inether, filtered and once more concentrated at reduced pressure.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 2/98).

Product:

White crystals.

Yield:

100%

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.52 (s, 9H, 3×CH₃); 1.64 (t, J=6.8 Hz,3H, CH₂CH₃); 4.69 (m, 2H, CH₃CH₂); 5.21 (d, J=10.0 Hz, 1H, NH); 6.32 (m,1H, CF₃CH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.6 (CH₃CH₂); 28.1 (3×CH₃); 57.8 (q,J=38 Hz, CF₃CH); 69.5 (C(CH₃)₃); 71.4 (CH₂CH₃); 120.4 (q, J=278 Hz,CF₃); 167.6 (C═O); 205.6 (C═S).

IR (ν, cm⁻¹) (CCl₄) 3441 (NH); 2983; 2358; 1737 (C═O); 1489; 1368; 1335;1236; 1193; 1153; 1123; 1048.

MP 80° C. (ethyl acetate-heptane) Mass (IC, NH₃) 320 (MH⁺), 337 (MNH₄⁺).

Microanalysis: Element Carbon Hydrogen Calculated (%) 37.61 5.05 Actual(%) 37.42 5.23

Radical Additions

General Operating Method:

A solution of xanthate (n mmol) and olefin (2n mmol) in1,2-dichloroethane (2n ml) is brought to reflux under argon for a fewminutes before lauroyl peroxide (LP) is added at a rate of from 2 to 5mol %/n every 90 minutes. Once the starting xanthate is completelyconsumed, the reaction medium is brought to ambient temperature thenconcentrated at reduced pressure before being purified.

Method for Preparing Compounds Having the Formula (IIA) RadicalAdditions Example 3 Ester ofS-[1-(2-acetylamino-3,3,3-trifluoro-propyl)-4-oxo-pentyl] dithiocarbonicacid O-ethyl ester

C₁₃H₂₀F₃NO₃S₂ M=359.43 g.mol⁻¹Reaction:

Carried out according to the general operating method with 160 mg (0.61mmol) of xanthate of example 1 and 142 μl (1.23 mmol) of hex-5-en-2-onein 2 ml of 1,2-dichloroethane. The reaction is terminated after theaddition of 5% of LP and 1 hour 30 minutes under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 1/1).

Product:

Pale yellow oil.

Yield:

88% (2 diastereoisomers at a ratio of 1/1)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.37 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.39 (t,J=7.0 Hz, 3H, CH₂CH₃); 1.67-1.86 (m, 2H); 1.90-2.16 (m, 6H); 1.98 (s,3H, COCH₃); 2.10 (s, 3H, COCH₃); 2.11 (s, 3H, COCH₃); 2.12 (s, 3H,COCH₃); 2.51-2.70 (m, 4H); 3.64 (m, 1H, CHS); 3.87 (m, 1H, CHS); 4.58(q, J=7.0 Hz, 2H, CH₃CH₂); 4.61 (q, J=7.0 Hz, 2H, CH₃CH₂); 4.75 (m, 1H,CF₃CH); 4.81 (m, 1H, CF₃CH); 6.35 (d, J=9.4 Hz, 1H, NH); 6.57 (d, J=10.0Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.78 (2 CH₃CH₂); 23.07 (2 CH₃CON);25.59 (CH₂); 29.16(CH₂); 29.97 (CH₃CO); 30.06 (CH₃CO); 32.74 (CH₂);34.19 (CH₂); 40.24 (CH₂); 40.61 (CH₂); 46.51 (CHS); 47.07 (CHS); 48.33(q, J=32 Hz, CF₃CH); 48.56 (q, J=30 Hz, CF₃CH); 70.49 (CH₂CH₃); 70.65(CH₂CH₃); 124.88 (q, J=281 Hz, CF₃); 125.10 (q, J=281 Hz, CF₃); 170.39(NC═O); 170.77 (NC═O); 207.32 (C═O); 208.15 (C═O); 213.69 (C═S); 214.09(C═S).

IR (ν, cm⁻¹) 3442 (NH); 2983; 1714 (C═O); 1703 (C═O); 1504; 1443; 1369;(CCl₄) 1238; 1185; 1133; 1112; 1050.

Mass (IC, NH₃) 360 (MH⁺), 377 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 43.44 5.61 Actual(%) 43.65 5.77

Example 4 Ester ofS-[5-(1-acetylamino-2,2,2-trifluoro-ethyl)-2-oxo-[1,3]dioxolan-4-yl]dithiocarbonic acid O-ethyl ester

Reaction:

Carried out according to the general operating method with 200 mg (0.77mmol) of xanthate of example 1 and 200 mg (2.31 mmol) of1,3-dioxol-2-one in 1.5 ml of 1,2-dichloroethane. The reaction isterminated after the addition of 20% of LP and 6 hours under reflux.

Purification:

Chromatography over silica gel (ether-petroleum ether 4/6 to 6/4).

Product:

First Diastereoisomer:

Rf (ether-petroleum ether 6/4)=0.30, pale yellow oil which slowlycrystallises over a period of time.

Second Diastereoisomer:

Rf (ether-petroleum ether 6/4)=0.16, colourless crystalline.

Yield:

72% (2 diastereoisomers at a ratio of 1/1)

First Diastereoisomer

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.46 (t, J=7.0 Hz, 3H, CH₂CH₃); 2.16 (s,3H, COCH₃); 4.69 (q, J=7.0 Hz, 2H, CH₃CH₂); 5.12 (d, J=5.3 Hz, 1H,CF3CH(NAc)CH); 5.17 (qd, J=7.6 Hz, 10.0 Hz, 1H, CF₃CH); 6.04 (d, J=5.3Hz, 1H, CHS); 7.38 (d, J=10.0 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.56 (CH₃CH₂); 22.61 (CH₃CO); 51.18(q, J=29 Hz, CF₃CH); 71.55 (CH₂CH₃); 77.68(CF3CH(NAc)CH); 83.55 (CHS);123.16 (q, J=283 Hz, CF₃); 152.95 (OC═O); 171.92 (NC═O); 205.72 (C═S).

IR (ν, cm⁻¹) (CCl₄) 3432 (NH); 3343 (NH); 2959; 1842; 1816 (C═O); 1741(C═O); 1709; 1500; 1709; 1500; 1371; 1273; 1236; 1192; 1141; 1047.

Mass (IC, NH₃) 348 (MH⁺); 365 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 34.58 3.48 Actual(%) 34.28 3.47Second Diastereoisomer

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.48 (t, J=7.0 Hz, 3H, CH₂CH₃); 2.13 (s,3H, COCH₃); 4.72 (q, J=7.0 Hz, 2H, CH₃CH₂); 4.85 (dd, J=5.3 Hz, 5.3 Hz,1H, CF₃CH(NAc)CH); 5.19 (qdd, J=7.6 Hz, 5.3 Hz, 10.0 Hz, 1H, CF₃CH);6.06 (d, J=10.0 Hz, 1H, NH); 6.35 (d, J=5.3 Hz, 1H, CHS).

¹³CNMR (δ, ppm) (CD₃OD, 100 MHz) 13.86 (CH₃CH₂); 22.40 (CH₃CO); 52.86(q, J=30 Hz, CF₃CH);72.75 (CH₂CH₃); 77.29 (CF₃CH(NAc)CH); 85.58 (CHS);125.03 (q, J=283 Hz, CF₃); 153.75 (OC═O); 173.66 (NC═O); 208.71 (C═S).

IR (ν, cm⁻¹)(CCl₄) 3258 (NH); 3064 (NH); 2985; 1818 (C═O); 1686; 1549;1442; 1360; 1298; 1255; 1135; 1076; 1047.

Mass (IC, NH₃) 348 (MH⁺); 365 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 34.58 3.48 Actual(%) 34.81 3.44

Example 5 Ester of3-acetylamino-1-ethoxythiocarbonylsulphanyl-4,4,4-trifluoro-butyl aceticacid

C₁₁H₁₆F₃NO₄S₂ M=347.38 g.mol⁻¹Reaction:

Carried out according to the general operating method with 200 mg (0.77mmol) of xanthate of example 1 and 85 μL (0.92 mmol) of vinyl acetate in1.5 ml of 1,2-dichloroethane. The reaction is terminated after theaddition of 2.5% of LP and 1 hour 30 minutes under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 2/8 to3/7).

Product:

Thick pale yellow oil which crystallises over a period of time

Yield:

95% (2 diastereoisomers at a ratio of 4/6)

¹H NMR (δ, ppm) (CDCl₃, 400 MHz) 1.38 (t, J=7.6 Hz, 3H, CH₂CH₃); 1.39(t, J=7.0 Hz, 3H, CH₂CH₃); 2.03 (s, 6H, COCH₃); 2.06 (s, 3H, COCH₃);2.07 (s, 3H, COCH₃); 2.12-2.22 (m, 2H, CF₃CH(NAc)CH₂); 2.38-2.51 (m, 2H,CF₃CH(NAc)CH₂); 4.60 (q, J=7.0 Hz, 2H, CH₃CH₂); 4.61 (q, J=7.6 Hz, 2H,CH₃CH₂); 4.70-4.83 (m, 2H, CF₃CH); 6.53 (dd, J=10.0 Hz, 2.9 Hz, 1H,CHS); 6.62 (d, J=9.4 Hz, 1H, NH); 6.64 (dd, J=8.2 Hz, 4.7 Hz, 1H, CHS);6.78 (d, J=10.0 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.60 (CH₃CH₂); 20.66 (CH₃CO); 20.77(CH₃CO); 22.80 (CH₃CO); 22.96 (CH₃CO); 32.66 (CH₂CHS); 33.33 (CH₂CHS);47.36 (q, J=32 Hz, CF₃CH); 47.65 (q, J=32 Hz, CF₃CH); 70.45 (CH₂CH₃);70.73 (CH₂CH₃); 76.00 (CHS); 78.30 (CHS); 124.63 (q, J=281 Hz, CF₃);124.71 (q, J=281 Hz, CF₃); 168.95 (C═O); 169.67 (C═O); 170.48 (C═O);170.72 (C═O); 209.33 (C═S); 209.86 (C═S).

IR (ν, cm⁻¹)(CCl₄) 3429 (NH); 2982; 1767 (C═O); 1706 (C═O); 1503; 1369;1235; 1188; 1137; 1049.

Mass (IC, NH₃) 288 (M-AcOH+H⁺); 348 (MH⁺); 365 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 38.03 4.64 Actual(%) 37.79 4.51

Example 6 Ester ofS-(3-acetylamino-4,4,4-trifluoro-1-trimethylsilanylmethyl-butyl)dithiocarbonic acid O-ethyl ester

C₁₃H₂₄F₃NO₂S₂Si M=375.55 g.mol⁻¹Reaction:

Carried out according to the general operating method with 200 mg (0.77mmol) of xanthate of example 1 and 364 μl (2.29 mmol) ofallyl-trimethyl-silane in 1.5 ml of 1,2-dichloroethane. The reaction isterminated after the addition of 5% of LP and 1 hour under reflux.

Purification:

Chromatograpy over silica gel (ethyl acetate-petroleum ether 1/9 to2/8).

Product:

First Diastereoisomer:

Rf (ethyl acetate-petroleum ether 1/9)=0.38, colourless crystallinesolid.

Second Diastereoisomer:

Rf (ethyl acetate-petroleum ether 1/9)=0.19, colourless crystallinesolid.

Yield:

95% (2 diastereoisomers at a ratio of 40/60)

First Diastereoisomer (Majority)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 0.03 (s, 9H, Si(CH₃)₃); 0.85-1.16 (m,2H, CH₂Si(CH₃)₃); 1.42 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.93-2.16 (m, 2H,CF3CH(NAc)CH₂); 2.11 (s, 3H, COCH₃); 3.64 (m, 1H, CHS); 4.63 (q, J=7.0Hz, 2H, CH₃CH₂); 4.71 (m, 1H, CF₃CH); 6.00 (d, J=9.4 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) −0.82 (Si(CH₃)₃); 13.87 (CH₃CH₂); 19.48(CH₂); 23.12 (CH₃CO); 37.37 (CH₂); 43.79 (CHS); 48.44 (q, J=32 Hz,CF₃CH); 70.29 (CH₂CH₃); 124.99 (q, J=281 Hz, CF₃); 170.34 (NC═O); 215.11(C═S).

IR (ν, cm⁻¹) (CCl₄) 3432 (NH); 2956; 1701 (C═O); 1507; 1250; 1218; 1184;1130; 1112; 1051.

Mass (IC, NH₃) 254 (M-HSCSOEt+H+); 376 (MH⁺);393 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 41.58 6.44 Actual(%) 41.48 6.41Second Diastereoisomer (Minority)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 0.07 (s, 9H, Si(CH₃)₃); 1.04-1.19 (m,2H, CH₂Si(CH₃)₃); 1.40 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.94-2.21 (m, 2H,CF₃CH(NAc)CH₂); 2.03 (s, 3H, COCH₃); 4.02 (m, 1H, CHS); 4.63 (q, J=7.0Hz, 2H, CH₃CH₂); 4.84 (m, 1H, CF₃CH); 6.03 (d, J=10.0 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) −0.68 (Si(CH₃)₃); 13.86 (CH₃CH₂); 23.18(CH₂); 23.26 (CH₃CO); 35.07 (CH₂); 44.98 (CHS); 48.50 (q, J=28 Hz,CF₃CH); 70.11 (CH₂CH₃); 125.13 (q, J=281 Hz, CF₃); 170.09 (NC═O); 213.53(C═S).

IR (ν, cm⁻¹) (CCl₄) 3441 (NH); 2955; 1704 (C═O); 1441; 1367; 1251; 1217;1183; 1129; 1112; 1048.

Mass (IC, NH₃) 254 (M-HSCSOEt+H⁺); 376 (MH⁺); 393 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 41.58 6.44 Actual(%) 41.49 6.45

Example 7 Ester of S-(3-acetylamino-1-cyanomethyl-4,4,4-trifluoro-butyl)dithiocarbonic acid O-ethyl ester

C₁₁H₁₅F₃N₂O₂S₂ M=328.38 g.mol⁻¹Reaction:

Carried out according to the general operating method with 200 mg (0.77mmol) of xanthate of example 1 and 184 μL (2.29 mmol) ofbut-3-enenitrile in 1.5 ml of 1,2-dichloroethane. The reaction isterminated after the addition of 15% of LP and 4 hours 30 minutes underreflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 3/7).

Product:

Thick pale yellow oil.

Yield:

87% (2 diastereoisomers at a ratio of 4/6).

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.39 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.40 (t,J=7.0 Hz, 3H, CH₂CH₃); 1.99 (s, 3H, COCH₃); 2.06 (s, 3H, COCH₃);2.02-2.31 (m, 4H, CF₃CH(NAc)CH₂); 2.82-3.02 (m, 4H, CH₂CN); 3.92 (m, 1H,CHS); 4.01 (m, 1H, CHS); 4.61 (q, J=7.0 Hz, 2H, CH₃CH₂); 4.63 (q, J=7.0Hz, 2H, CH₃CH₂); 4.73 (m, 1H, CF₃CH); 4.82 (m, 1H, CF₃CH); 6.90 (d,J=10.0 Hz, 1H, NH); 7.01 (d, J=9.4 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.66 (CH₃CH₂); 22.28 (CH₂); 22.79(CH₃CO); 24.21 (CH₂); 30.40 (CH₂); 31.39 (CH₂); 42.48 (CHS); 43.11(CHS); 48.20 (q, J=30 Hz, CF₃CH); 48.27 (q, J=30 Hz, CF₃CH); 70.98(CH₂CH₃); 71.14 (CH₂CH₃); 116.53 (CN); 116.90 (CN); 124.52 (q, J=281 Hz,CF₃); 124.71 (q, J=281 Hz, CF₃); 170.93 (C═O); 171.24 (C═O); 211.24(C═S); 211.34 (C═S).

IR (ν, cm⁻¹)(CCl₄) 3438 (NH); 2984; 1701 (C═O); 1505; 1442; 1369; 1237;1191; 1139; 1112; 1049.

Mass (IC, NH₃) 329 (MH⁺); 346 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 40.23 4.60 Actual(%) 40.39 4.53

Example 8 Ester ofS-(3-acetylamino-1-diethoxymethyl-4,4,4-trifluoro-butyl) dithiocarbonicacid O-ethyl ester

C₁₄H₂₄F₃NO₄S₂ M=391.47 g.mol⁻¹Reaction:

Carried out according to the general operating method with 200 mg (0.77mmol) of xanthate of example 1 and 351 μL (2.29 mmol) of3,3-diethoxy-propene in 1.5 ml of 1,2-dichloroethane. The reaction isterminated after the addition of 5% of LP and 1 hour 30 minutes underreflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 3/7).

Product:

Thick pale yellow oil.

Yield:

95% (2 diastereoisomers at a ratio of 1/1).

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.16 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.17 (t,J=7.0 Hz, 3H, CH₂CH₃); 1.20 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.21 (t, J=7.0Hz, 3H, CH₂CH₃); 1.38 (t, J=7.0 Hz, 6H, CH₂CH₃); 1.80-2.19 (m, 3H,CF₃CH(NAc)CH₂); 1.98 (s, 3H, COCH₃); 2.05 (s, 3H, COCH₃); 2.49 (m, 1H,CF₃CH(NAc)CH₂); 3.43-3.76 (m, 8H, CH₃CH₂); 3.95-4.05 (m, 2H, CHS); 4.52(d, J=3.0 Hz, 1H, CH(OEt)₂); 4.59 (d, J=3.0 Hz, 1H, CH(OEt)₂); 4.61 (q,J=7.0 Hz, 4H, CH₃CH₂); 4.73-4.91 (m, 2H, CF₃CH); 6.19 (d, J=9.4 Hz, 1H,NH); 6.31 (d, J=9.4 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.78 (2×CH₃CH₂); 15.08 (2×CH₃CH₂);15.15 (CH₃CH₂); 15.34 (CH₃CH₂); 23.04 (CH₃CO); 23.13 (CH₃CO); 25.80(CH₂CHS); 28.46 (CH₂CHS); 48.42 (q, J=30 Hz, CF₃CH); 49.08 (q, J=30 Hz,CF₃CH); 49.88 (CHS); 50.44 (CHS); 64.09 (CH₂CH₃); 64.31 (CH₂CH₃); 64.76(CH₂CH₃); 65.54 (CH₂CH₃); 70.54 (CH₂CH₃); 70.63 (CH₂CH₃);102.75(CH(OEt)₂); 103.95 (CH(OEt)₂); 124.94 (q, J=281 Hz, CF₃); 125.17 (q,J=283 Hz, CF₃); 170.14 (C═O); 171.32 (C═O); 213.91 (C═S); 214.79 (C═S).

IR (ν, cm⁻¹) (CCl₄) 3443 (NH); 2979; 2930; 2875; 1741 (C═O); 1703 (C═O);1508; 1443; 1370; 1341; 1284; 1218; 1185; 1135; 1112; 1054.

Mass (IC, NH₃) 346 (M-EtOH+H⁺).

Example 9 Ester ofS-[3-acetylamino-1-(1,3-dioxo-1,3-dihydro-isoindol-2-ylmethyl)-4,4,4-trifluoro-butyl]dithiocarbonic acid O-ethyl ester

C₁₈H₁₉F₃N₂O₄S₂ M=448.48 g.mol⁻¹Reaction:

Carried out according to the general operating method with 200 mg (0.77mmol) of xanthate of example 1 and 286 mg (1.53 mmol) of allylphthalimide in 1.5 ml of 1,2-dichloroethane. The reaction is terminatedafter the addition of 10% of LP and 3 hours under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 4/6).

Product:

Colourless crystalline.

Yield:

77% (2 diastereoisomers at a ratio of 6/4)

¹H NMR (δ, ppm) (CDCl₃, 400 MHz) 1.33 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.37(t, J=7.0 Hz, 3H, CH₂CH₃); 2.02-2.24 (m, 4H, CF₃CH(NAc)CH₂); 2.02 (s,3H, COCH₃); 2.19 (s, 3H, COCH₃); 3.93-4.06 (m, 4H, CH₂N); 4.16-4.23 (m,1H, CHS); 4.23-4.30 (m, 1H, CHS); 4.51 (q, J=7.0 Hz, 2H, CH₃CH₂); 4.57(q, J=7.0 Hz, 2H, CH₃CH₂); 4.90-5.11 (m, 2H, CF₃CH); 6.44 (d, J=10.0 Hz,1H, NH); 6.53 (d, J=10.0 Hz, 1H, NH); 7.70-7.73 (m, 4H, H_(Ar.));7.79-7.84 (m, 4H, H_(Ar.)).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.62 (CH₃CH₂); 13.71 (CH₃CH₂); 23.13(CH₃CO); 23.19 (CH₃CO); 23.96 (CF₃CH(NAc)CH₂); 30.42 (CF₃CH(NAc)CH₂);39.03 (CH₂N); 41.56 (CH₂N); 45.89 (CHS); 46.34 (CHS); 48.24 (q, J=31 Hz,CF₃CH); 48.62 (q, J=31 Hz, CF₃CH); 70.68 (CH₂CH₃); 70.71 (CH₂CH₃);123.52 (CH_(Ar.)); 123.61 (CH_(Ar.)); 124.85 (q, J=279 Hz, CF₃); 124.99(q, J=280 Hz, CF₃); 131.67 (Cq_(Ar.)); 131.72 (Cq_(Ar.)); 134.36(2×CH_(Ar.)); 168.17 (2×C═O_(Ar.)); 168.24 (2×C═O_(Ar.)); 170.34 (C═O);170.75 (C═O); 211.9 (C═S); 212.75 (C═S).

IR (ν, cm⁻¹) (CCl₄) 3441 (NH); 2983; 1776 (C═O); 1722 (C═O); 1504; 1468;1441; 1392; 1366; 1227; 1187; 1134; 1112; 1050.

Mass (IC, NH₃) 449 (MH⁺); 366 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 48.21 4.27 Actual(%) 48.61 4.42

Example 10 Ester of diethyl(4-acetylamino-2-ethoxythiocarbonylsulphanyl-5,5,5-trifluoro-pentyl)phosphonic acid

C₁₄H₂₅F₃NO₅PS₂ M=439.45 g.mol⁻¹Reaction:

Carried out according to the general operating method with 200 mg (0.77mmol) of xanthate of example 1 and 407 mg (2.29 mmol) of diethylallylphosphonic acid ester in 1.5 ml of 1,2-dichloroethane. The reactionis terminated after the addition of 5% of LP and 1 hour 30 minutes underreflux.

Purification:

Chromatography over silica gel (dichloromethane-methanol 99/1).

Product:

Pale yellow oil.

Yield:

86% (2 diastereoisomers at a ratio of 6/4)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.29 (t, J=7.6 Hz, 6H, CH₂CH₃); 1.30 (t,J=7.0 Hz, 6H, CH₂CH₃); 1.25 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.36 (t, J=7.0Hz, 3H, CH₂CH₃); 1.99 (s, 3H, COCH₃); 2.02 (s, 3H, COCH₃); 2.06-2.45 (m,8H, CH₂P+CF₃CH(NAc)CH₂); 3.92-4.16 (m, 10 H, CH₃CH₂+CHS); 4.53-4.61 (m,4H, CH₃CH₂); 4.65-4.79 (m, 2H, CF₃CH); 7.05 (d, J=8.8 Hz, 1H, NH); 7.10(d, J=9.4 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.68 (2×CH₃CH₂); 16.34 (m, CH₃CH₂OP);22.90 (2×CH₃CO); 29.02 (d, J=138 Hz, CH₂P); 31.26 (CF₃CH (NAc)CH₂);31.45 (CF₃CH(NAc)CH₂); 31.75 (d, J=135 Hz, CH₂P); 41.52 (CHS); 42.09(CHS); 48.37 (q, J=30 Hz, CF₃CH); 48.68 (q, J=30 Hz, CF₃CH); 62.21 (m,CH₃CH₂OP); 70.35 (2×CH₂CH₃); 124.85 (2×q, J=281 Hz, CF₃); 170.51 (C═O);170.67 (C═O); 212.20 (C═S); 212.87 (C═S).

IR (ν, cm⁻¹) (CCl₄) 3309 (NH); 2983; 1699 (C═O); 1532; 1442; 1390; 1368;1291; 1227; 1186; 1135; 1112; 1048; 1028.

Mass (IC, NH₃) 318 (M-HSCSOEt+H⁺); 440 (MH⁺); 457 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 38.26 5.73 Actual(%) 38.01 5.81

Example 11 Ester of4-acetylamino-2-ethoxythiocarbonylsulphanyl-5,5,5-trifluoro-pentylacetic acid

C₁₂H₁₈F₃NO₄S₂ M=361.40 g.mol⁻¹Reaction:

Carried out according to the general operating method with 200 mg (0.77mmol) of xanthate of example 1 and 247 μL (3 mmol) of allyl acetate in1.5 ml of 1,2-dichloroethane. The reaction is terminated after theaddition of 5% of LP and 1 hour 30 minutes under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 3/7).

Product:

Pale yellow oil.

Yield:

84% (2 diastereoisomers at a ratio of 1/1).

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.38 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.40 (t,J=7.0 Hz, 3H, CH₂CH₃); 1.89-2.15 (m, 3H, CF₃CH(NAc)CH₂); 1.99 (s, 3H,COCH₃); 2.06 (s, 3H, COCH₃); 2.07 (s, 3H, COCH₃); 2.08 (s, 3H, COCH₃);2.20-2.27 (m, 3H, CF₃CH(NAc)CH₂); 3.92-3.98 (m, 1H, CHS); 4.09-4.15 (m,1H, CHS); 4.24-4.41 (m, 4H, CH₂OCOCH₃); 4.60 (q, J=7.0 Hz, 2H, CH₃CH₂);4.62 (q, J=7.0 Hz, 2H, CH₃CH₂); 4.72-4.91 (m, 2H, CF₃CH); 6.50 (d, J=9.4Hz, 1H, NH); 6.64 (d, J=9.4 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.71 (CH₃CH₂); 13.73 (CH₃CH₂); 20.69(CH₃CO); 20.78 (CH₃CO); 22.97 (CH₃CO); 22.99 (CH₃CO); 29.04(CF₃CH(NAc)CH₂); 30.12 (CF₃CH(NAc)CH₂); 45.62 (CHS); 46.00 (CHS); 48.36(q, J=30 Hz, CF₃CH); 48.49 (q, J=30 Hz, CF₃CH); 63.98 (CH₂OCOCH₃); 65.94(CH₂OCOCH₃); 70.71 (CH₂CH₃); 70.83 (CH₂CH₃); 124.75 (q, J=281 Hz, CF₃);124.99 (q, J=281 Hz, CF₃); 170.49 (C═O); 170.64 (C═O); 170.75 (C═O);170.86 (C═O); 212.39 (C═S); 212.94 (C═S).

IR (ν, cm⁻¹)(CCl₄) 3442 (NH); 2984; 1752 (C═O); 1703 (C═O); 1506; 1442;1381; 1367; 1340; 1227; 1186; 1137; 1112; 1052.

Mass (IC, NH₃) 302 (M-HOAc+H⁺); 362 (MH⁺); 379 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 39.88 5.02 Actual(%) 40.08 5.07

Example 12 Ester ofS-[3-acetylamino-4,4,4-trifluoro-1-(2-oxo-pyrrolidin-1yl)-butyl]dithiocarbonic acid O-ethyl ester

C₁₃H₁₉F₃N₂O₃S₂ M=372.43 g.mol⁻¹Reaction:

Carried out according to the general operating method with 200 mg (0.77mmol) of xanthate of example 1 and 104 μL (mmol) ofvinyl-pyrrolidin-2-one in 1.5 ml of 1,2-dichloroethane. The reaction isterminated after the addition of 10% of LP and 3 hours under reflux.

Purification:

Chromatography over silica gel (dichloromethane-methanol 98/2).

Product:

Unstable pale yellow oil which leads to the enamide of example 13.

Yield:

62% (2 diastereoisomeres at a ratio of 4/6) 21% of the enamide ofexample 13

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.41 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.42 (t,J=7.0 Hz, 3H, CH₂CH₃); 2.02-2.26 (m, 7H, CH₂CO+CF₃CH(NAc)CH₂); 2.07 (s,3H, COCH₃); 2.09 (s, 3H, COCH₃); 2.35-2.42 (m, 4H, CH₂CH₂CH₂); 2.60-2.67(m, 1H, CF₃CH(NAc)CH₂); 3.41-3.57 (m, 4H, CH₂N); 4.50-4.62 (m, 1H,CF₃CH); 4.64 (q, J=7.0 Hz, 2H, CH₃CH₂); 4.65 (q, J=7.0 Hz, 2H, CH₃CH₂);4.74-4.86 (m, 1H, CF₃CH); 5.90 (dd, J=12.3 Hz, 4.1 Hz, 1H, CHS); 6.02(dd, J=8.2 Hz, 7.6 Hz, 1H, CHS); 6.69 (d, J=10.0 Hz, 1H, NH); 7.29 (d,J=10.0 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.68 (CH₃CH₂); 13.76 (CH₃CH₂); 18.00(CH₂CH₂CH₂); 18.15(CH₂CH₂CH₂); 22.94 (CH₃CO); 23.02 (CH₃CO); 30.66(CH₂CO); 30.84 (CH₂CO); 31.06 (CF₃CH(NAc)CH₂); 31.25 (CF₃CH(NAc)CH₂);44.95 (CH₂N); 45.24 (CH₂N); 47.49 (q, J=30 Hz, CF₃CH); 48.08 (q, J=32Hz, CF₃CH); 58.33 (CHS); 58.98 (CHS); 70.62 (CH₂CH₃); 70.71 (CH₂CH₃);124.75 (q, J=281 Hz, CF₃); 124.82 (q, J=282 Hz, CF₃); 170.54 (C═O);170.86 (C═O); 175.52 (C═O); 175.57 (C═O); 210.06 (C═S); 211.76 (C═S).

IR (ν, cm⁻¹) (CCl₄) 3439 (NH); 3298 (NH); 2984; 1703 (C═O); 1501; 1416;1368; 1286; 1265; 1226; 1183; 1132; 1111; 1049.

Mass (IC, NH₃) 251 (M-HSCSOEt+H⁺); 268 (M-HSCSOEt+NH₄ ⁺); 373 (MH⁺); 390(MNH₄ ⁺).

Example 13 Ester ofS-[3-acetylamino-1-{[(4-bromo-phenyl)-methanesulphonyl-amino]-methyl}-4,4,4-trifluoro-butyl]dithiocarbonic acid O-ethyl ester

C₁₇H₂₂BrF₃N₂O₄S₃ M=551.463 g.mol⁻¹Reaction:

Carried out according to the general operating method with 261 mg (1mmol) of xanthate of example 1 and 580 mg (2 mmol) ofN-allyl-N-(4-bromo-phenyl)-methanesulphonamide in 2 ml of1,2-dichloroethane. The reaction is terminated after the addition of 20%of LP and 7 hours under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 4/6).

Product:

White foam.

Yield:

77% (2 diastereoisomers at a ratio of 1/1)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.29 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.33 (t,J=7.0 Hz, 3H, CH₂CH₃); 1.86 (s, 3H, COCH₃); 1.90-2.04 (m, 2H,CF₃CH(NAc)CH₂); 1.94 (s, 3H, COCH₃); 2.19-2.30 (m, 2H, CF₃CH(NAc)CH₂);2.83 (s, 6H, SO₂CH₃); 3.56-3.70 (m, 2H, CHS); 3.81-3.96 (m, 4H, CH₂N);4.44-4.57 (m, 4H, CH₃CH₂); 4.70-4.83 (m, 2H, CF₃CH); 6.50 (d, J=9.4 Hz,1H, NH); 6.67 (d, J=9.4 Hz, 1H, NH); 7.20 (d, J=8.2 Hz, 2H,H_(Ar)(HC═CNSO₂)); 7.30 (d, J=8.2 Hz, 2H, H_(Ar)(HC═CNSO₂)); 7.51 (d,J=8.2 Hz, 2H, H_(Ar)(HC═CBr)); 7.54 (d, J=8.2 Hz, 2H, H_(Ar)(HC═CBr)).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.53 (CH₃CH₂); 13.61 (CH₃CH₂); 22.64(CH₃CO); 22.75 (CH₃CO); 28.18 (CF₃CH(NAc)CH₂); 29.52 (CF₃CH(NAc)CH₂);36.70 (CH₃SO₂); 36.97 (CH₃SO₂); 44.84 (CHS); 45.67 (CHS); 48.03 (q, J=32Hz, 2×CF₃CH); 51.40 (CH₂N); 53.37 (CH₂N); 70.61 (2×CH₂CH₃); 122.64(2×Cq_(Ar.)Br); 124.64 (q, J=281 Hz, CF₃); 124.79 (q, J=281 Hz, CF₃);130.32 (CH_(Ar.)); 130.43 (CH_(Ar.)); 132.73 (2×CH_(Ar.)); 137.14(Cq_(Ar.)NSO₂); 137.31 (Cq_(Ar.)NSO₂); 170.43 (C═O); 170.72 (C═O);211.49 (C═S); 212.54 (C═S).

IR (ν, cm⁻¹) (CCl₄) 3437 (NH); 2984; 1700 (C═O); 1488; 1442; 1358; 1227;1187; 1162; 1140; 1112; 1050; 1012.

Mass (IC, NH₃) 552 (MH⁺); 569 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 37.03 4.02 Actual(%) 37.06 4.11

Example 14 Ester dithiocarbonic acidS-[1-(2-acetylamino-3,3,3-trifluoro-propyl)-2-phenyl-cyclopropane]O-ethyl

C₁₇H₂₀F₃NO₅S₂ M=391.48 g.mol⁻¹Reaction:

Carried out according to the general operating method with 131 mg (0.50mmol) of xanthate of example 1 and 130 mg (1.00 mmol) of1-methylen-2-phenylcyclopropane in 1,2-dichloroethane (2 ml). Thereaction is terminated after the addition of 10% of LP (20 mg) and 3hours under reflux.

Purification:

Chromatography over silica gel (ether-petroleum ether 3/7).

Product:

First Diastereoisomer:

Rf (ether-petroleum ether 3/7)=0.20, pale yellow oil which crystallisesslowly.

Second Diastereoisomer:

Rf (ether-petroleum ether 3/7)=0.16, pale yellow oil.

Yield:

68% (2 diastereoisomers at a ratio of 3/1)

First Diastereoisomer (Majority):

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.46 (t, J=5.0 Hz, 3H, CH₂CH₃); 1.86 (s,3H, COCH₃); 2.05 (d, J=7.0 Hz, 2H, CH₂CHC_(Ar.)); 1.86-2.16 (m, 2H,CH₂CHCF₃); 2.71 (dd, J₁=8.0 Hz, J₂=0.8 Hz, 1H, CHC_(Ar.)); 4.59-4.64 (m,2H, CH₃CH₂); 4.64-4.68 (m, 1H, CHCF₃); 5.06 (d, J=9.4 Hz, 1H, NH);7.20-7.50 (m, 5H, H_(Ar.)).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.6 (CH₃CH₂); 16.6 (CH₃CO); 21.9(CH₂CHCF₃); 28.8 (CH₂CHC_(Ar.)); 31.1 (CHC_(Ar.)); 32.8 (Cq_(cyclo.));49.9 (q, J=29 Hz, CF₃CH); 70.1 (OCH₂CH₃); 124.2 (CF₃); 129.6(2×CH_(Ar.)); 130.0 (2×CH_(Ar.)); 130.8 (CH_(Ar.)); 138.4 (Cq_(Ar.));170.9 (NC═O); 212.7 (C═S).

IR (ν, cm⁻¹)(CCl₄) 3432 (NH); 2927; 1702 (C═O); 1498; 1225; 1224 (C═S);1221; 1124; 1051.

Mass (IC, NH3) 392 (MH⁺); 409 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 52.16 5.15 Actual(%) 52.25 5.08

MP 137° C. (ethyl acetate-heptane)

Second Diastereoisomer (Minority):

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.36 (t, J=5.0 Hz, 3H, CH₂CH₃); 1.96 (s,3H, COCH₃); 2.45 (d, J=12.0 Hz, 2H, CH₂CHC_(Ar.)); 1.96-2.43 (m, 2H,CH₂CHCF₃); 2.83 (dd, J₁=5.7 Hz, J₂=0.8 Hz, 1H, CHC_(Ar.)); 4.64-4.69 (m,2H, CH₃CH₂); 4.89-4.98 (m, 1H, CHCF₃); 6.25 (d, J=11.4 Hz, 1H, NH);7.10-7.50 (m, 5H, H_(Ar.)).

¹³CNMR (δ, ppm) (CD₃OD, 100 MHz) 13.9 (CH₃CH₂); 16.7 (CH₃CO); 32.5(Cq_(cyclo.)); 31.1 (CHC_(Ar.)) 28.6 (CH₂CHC_(Ar.)); 21.9 (CH₂CHCF₃);49.6 (q, J=29 Hz, CF₃CH); 70.2 (OCH₂CH₃); 124.1 (CF₃); 129.5(2×CH_(Ar.)); 129.9 (2×CH_(Ar.)); 130.3 (CH_(Ar.)); 138.3 (Cq_(Ar.));170.5 (NC═O); 212.8 (C═S).

IR (ν, cm⁻¹) (CCl₄) 3432 (NH); 2927; 1702 (C═O); 1498; 1225; 1224 (C═S);1221; 1124; 1051.

Mass (IC, NH3) 392 (MH⁺); 409 (MNH₄ ⁺).

Example 15 Ester of4-benzoylamino-2-ethoxythio-carbonyl-sulphanyl-5,5,5-trifluoro-butylacetic acid

C₁₇H₂₀F₃NO₄S₂ M=423.08 g.mol⁻¹Reaction:

Carried out according to the general operating method with 500 mg (1.55mmol) of xanthate S-(1-benzoylamino-2,2,2-trifluoro-ethyl) esterdithiocarbonic acid O-ethyl ester [operating method of the xanthate tobe provided] and 333 μL (3 mmol) of allyl acetate in 1,2-dichloroethane(3 ml). The reaction is terminated after the addition of 10% of LP (62mg) and 1 hour 30 minutes under reflux.

Purification:

Chromatography over silica gel (ether-petroleum ether 3/7).

Product:

Pale yellow oil.

Yield:

84% (admixture of 2 diastereoisomers at a ratio of 1/1).

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.32 (t, J=7.0 Hz, 1.5H, CH₂CH₃); 1.38(t, J=7.0 Hz, 1.5H, CH₂CH₃); 1.89-2.15 (m, 1H, CF₃CHNCH₂); 1.99 (s,1.5H, COCH₃); 2.06 (s, 1.5H, COCH₃); 2.20-2.27 (m, 1H, CF₃CHNCH₂);3.92-3.98 (m, 0.5H, CHS); 4.09-4.15 (m, 0.5H, CHS); 4.24-4.41 (m, 2H,CH₂OCOCH₃); 4.52 (q, J=6.1 Hz, 1H, CH₃CH₂); 4.54 (q, J=5.0 Hz, 1H,CH₃CH₂); 4.98-5.12 (m, 1H, CF₃CH); 6.20 (d, J=8.7 Hz, 0.5H, NH); 6.54(d, J=8.9 Hz, 0.5H, NH); 7.31-7.92 (m, 5H, CH_(Ar.)).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.7 (CH₃CH₂); 22.9 (CH₃CO); 29.0(0.5×CF₃CHCH₂); 30.1 (0.5×CF₃CHCH₂); 45.6 (0.5×CHS); 46.0 (0.5×CHS);48.3 (q, J=30 Hz, 0.5×CF₃CH); 48.4 (q, J=30 Hz, 0.5×CF₃CH); 63.9(0.5×CH₂OCOCH₃); 65.9 (0.5×CH₂OCOCH₃); 70.7 (0.5×CH₂CH₃); 70.8(0.5×CH₂CH₃); 124.5 (q, J=281 Hz, 0.5×CF₃); 124.9 (q, J=281 Hz,0.5×CF₃); 132.5 (2.5×CH_(Ar.)); 133.7 (2.5×CH_(Ar.)); 145.4(0.5×Cq_(Ar.)); 146.3 (0.5×Cq_(Ar.)); 170.4 (0.5×OC═O); 170.6(0.5×OC═O); 170.7 (0.5×C═O); 170.8 (0.5×C═O); 212.3 (0.5×C═S); 212.9(0.5×C═S).

IR (ν, cm⁻¹) (CCl₄) 3442 (NH); 2984; 1752 (OC═O); 1703 (NC═O); 1506;1442; 1381; 1367; 1340; 1224 (C═S); 1186; 1137; 1112; 1052.

Mass (IC, NH3) 424 (MH⁺); 441 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 48.22 4.76 Actual(%) 48.08 4.83

Example 164-tertbutyloxycarbamate-2-ethoxythiocarbonylsulphanyl-5,5,5-trifluoro-pentylicester of acetic acid

C₁₅H₂₄F₃NO₅S₂ M=419.49 g.mol⁻¹Reaction:

Carried out according to the general operating method with 50 mg (0.2mmol) of xanthate of example 2 and 32 mg (0.4 mmol) of allyl acetate in1,2-dichloroethane (1 ml). The reaction is terminated after the additionof 15% of LP (12 mg) and 4 hours 30 minutes under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 5/95).

Product:

Pale yellow oil.

Yield:

76% (2 diastereoisomers at a ratio of 1/1)

First Diastereoisomer:

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.38 (t, J=7.0 Hz, 3H, CH₂CH₃); 2.0 (s,9H, 3×CH₃); 2.12 (s, 3H, COCH₃); 2.18-2.25 (m, 2H, CF₃CHNCH₂); 3.97-4.05(m, 1H, CHS); 4.30 (dd, J₁=2.9 Hz, J₂=12.2 Hz, 1H, 1×CH₂OCOCH₃); 4.49(dd, J₁=2.9 Hz, J₂=12.2 Hz, 1H, 1×CH₂OCOCH₃); 4.61 (q, J=5.9 Hz, 1H,CF₃CH); 4.65 (q, J=7.0 Hz, 2H, CH₃CH₂); 4.92 (d, J=11.7 Hz, 1H, NH).

NMR¹³C (δ, ppm) (CDCl₃, 100 MHz) 13.7 (CH₃CH₂); 18.3 (3×CH₃); 28.6(CH₃CO); 30.1 (CF₃CHNCH₂); 46.0 (CHS); 48.5 (q, J=30 Hz, CF₃CH); 65.9(CH₂OCOCH₃); 70.8 (CH₂CH₃); 125.0 (q, J=281 Hz, CF₃); 152.2 (C(CH₃)₃);170.6 (C═O); 170.9 (C═O); 212.7 (C═S).

IR (ν, cm⁻¹) (CCl₄) 3442 (NH); 2983; 1753 (C═O); 1422; 1263; 894; 869.

Mass (IC, NH3) 420 (MH⁺); 437 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 42.95 5.77 Actual(%) 42.92 5.78Second Diastereoisomer:

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.38 (t, J=7.0 Hz, 3H, CH₂CH₃); 2.05 (s,9H, 3×CH₃); 2.14 (s, 3H, COCH₃); 2.19-2.22 (m, 2H, CF₃CHNCH₂); 4.05-4.12(m, 1H, CHS); 4.32 (dd, J₁=2.9 Hz, J₂=12.2 Hz, 1H, 1×CH₂OCOCH₃); 4.42(dd, J₁=2.9 Hz, J₂=12.2 Hz, 1H, 1×CH₂OCOCH₃); 4.56 (q, J=5.8 Hz, 1H,CF₃CH); 4.62 (q, J=7.0 Hz, 2H, CH₃CH₂); 4.75 (d, J=12.4 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.7 (CH₃CH₂); 18.5 (3×CH₃); 28.4(CH₃CO); 29.0 (CF₃CHNCH₂); 45.6 (CHS); 48.5 (q, J=30 Hz, CF₃CH); 64.0(CH₂OCOCH₃); 70.7 (CH₂CH₃); 124.7 (q, J=281 Hz, CF₃); 152.4 (C(CH₃)₃);170.5 (C═O); 170.7 (C═O); 212.4 (C═S).

IR (ν, cm⁻¹) (CCl₄) 3442 (NH); 2983; 1732 (C═O); 1422; 1263; 894; 869.

Mass (IC, NH3) 420 (MH⁺); 437 (MNH₄ ⁺).

Example 17 O-ethyl andS-(3-tertbutyloxycarbamate-1-diethoxy-methyl-4,4,4-trifluoro-butyl esterof dithiocarbonic acid

C₁₇H₃₀F₃NO₅S₂ M=448.57 g.mol⁻¹Reaction:

Carried out according to the general operating method with 50 mg (0.2mmol) of xanthate of example 2 and 48 μL (0.4 mmol) of3,3-diethoxy-propene in 1,2-dichloroethane (1 ml). The reaction isterminated after the addition of 15% of LP (12 mg) and 4 hours 30minutes under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 5/95).

Product:

Thick pale yellow oil.

Yield:

94% (admixture of 2 diastereoisomers at a ratio of 1/1)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.23 (t, J=6.1 Hz, 1.5H, CH₂CH₃); 1.25(t, J=6.1 Hz, 1.5H, CH₂CH₃); 1.26 (t, J=6.1 Hz, 1.5H, CH₂CH₃); 1.28 (t,J=6.1 Hz, 1.5H, CH₂CH₃); 1.45 (t, J=6.1 Hz, 3H, CH₂CH₃); 1.52 (s, 4.5H,C(CH₃)₃); 1.56 (s, 4.5H, C(CH₃)₃); 1.75 (dd, J₁=4.0 Hz, J₂=14.2 Hz,0.5H, CF₃CHNCH₂); 1.85 (dd, J₁=4.0 Hz, J₂=14.2 Hz, 0.5H, CF₃CHNCH₂);2.15 (dd, J₁=4.0 Hz, J₂=14.2 Hz, 0.5H, CF₃CHNCH₂); 2.55 (dd, J₁=4.0 Hz,J₂=14.2 Hz, 0.5H, CF₃CHNCH₂); 3.53 (q, J=6.0 Hz, 1H, CH₃CH₂O); 3.55 (q,J=6.0 Hz, 1H, CH₃CH₂O); 3.63 (q, J=6.0 Hz, 1H, CH₃CH₂O); 3.78 (q, J=6.0Hz, 1H, CH₃CH₂O); 3.85-4.02 (m, 1H, CHS); 4.06-4.12 (m, 1H, CH(OEt)₂);4.48-4.51 (m, 1H, CF₃CH); 4.63 (q, J=6.1 Hz, 1H, CH₃CH₂); 4.73 (q, J=6.1Hz, 1H, CH₃CH₂); 4.81 (d, J=12.2 Hz, 0.5H, NH); 4.83 (d, J=12.2 Hz,0.5H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.8 (CH₃CH₂); 15.2 (CH₃CH₂); 15.2(0.5×CH₃CH₂); 15.3 (0.5×CH₃CH₂); 19.5 (3×CH₃); 25.8 (0.5×CH₂CHS); 28.5(0.5×CH₂CHS); 48.4 (q, J=30 Hz, 0.5×CF₃CH); 49.0 (q, J=30 Hz,0.5×CF₃CH); 49.9 (0.5×CHS); 50.4 (0.5×CHS); 64.0 (0.5×CH₂CH₃); 64.3(0.5×CH₂CH₃); 64.7 (0.5×CH₂CH₃); 65.5 (0.5×CH₂CH₃); 70.5 (0.5×CH₂CH₃);70.6 (0.5×CH₂CH₃); 102.7 (0.5×CH(OEt)₂); 103.9 (0.5×CH(OEt)₂); 124.9 (q,J=281 Hz, 0.5×CF₃); 125.1 (q, J=281 Hz, 0.5×CF₃); 150.4 (0.5×C(CH₃)₃);151.2 (0.5×C(CH₃)₃); 170.1 (0.5×C═O); 171.3 (0.5×C═O); 213.9 (0.5×C═S);214.7 (0.5×C═S).

IR (ν, cm⁻¹) (CCl₄) 3443 (NH); 2976; 2905; 2805; 1734 (C═O); 1720 (C═O);1594; 1246; 1213; 1180; 1168; 1070.

Mass (IC, NH3) 402 (MH⁺-EtOH).

Microanalysis Element: Carbon Hydrogen Calculated (%) 48.20 6.97 Actual(%) 47.05 6.93

Example 18 O-ethyl andS-(3-tertbutyl-oxycarbamate-1-diethoxy-methyl-4,4,4-trifluoro-butyl)diester of dithiocarbonic acid

C₁₈H₃₂F₃NO₅S₂ M=463.58 g.mol⁻¹Reaction:

Carried out according to the general operating method with 200 mg (0.6mmol) of xanthate of example 2 and 181 mg (1.25 mmol) of4,4-diethoxy-butene in 1,2-dichloroethane (2 ml). The reaction isterminated after the addition of 15% of LP (36 mg) and 4 hours 30minutes under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 5/95).

Product:

Thick pale yellow oil.

Yield:

72% (admixture of 2 diastereoisomers at a ratio of 1/1)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 0.92 (dd, J₁=8.8 Hz, J₂=13.3 Hz, 1H,SCH—CH₂—CH); 0.95 (dd, J₁=8.8 Hz, J₂=13.3 Hz, 1H, SCH—CH₂—CH); 1.20 (t,J=7.0 Hz, 1.5H, CH₂CH₃); 1.25 (t, J=7.0 Hz, 1.5H, CH₂CH₃); 1.26 (t,J=7.0 Hz, 1.5H, CH₂CH₃); 1.28 (t, J=7.0 Hz, 1.5H, CH₂CH₃); 1.45 (t,J=7.0 Hz, 3H, CH₂CH₃); 1.52 (s, 4.5H, C(CH₃)₃); 1.56 (s, 4.5H, C(CH₃)₃);1.98-2.07 (m, 1H, CF₃CHNCH₂); 2.08-2.15 (m, 1H, CF₃CHNCH₂); 3.68-3.74(m, 2H, CH₃CH₂O); 3.79-3.82 (m, 2H, CH₃CH₂O); 3.92-3.99 (m, 1H,CH(OEt)₂); 4.02-4.13 (m, 1H, CHS); 4.43-4.51 (m, 1H, CF₃CH); 4.59-4.65(m, 1H, CH₃CH₂O); 3.64-3.67 (m, 1H, CH₃CH₂O); 6.01 (d, J=12.0 Hz, 0.5H,NH); 6.13 (d, J=12.0 Hz, 0.5H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.7 (CH₃CH₂); 13.8 (CH₃CH₂); 15.1(0.5×CH₃CH₂); 15.3 (0.5×CH₃CH₂); 19.8 (3×CH₃); 21.1 (0.5×CH—CH₂—CH);21.3 (0.5×CH—CH₂—CH); 28.5 (0.5×CH₂CHS); 28.7 (0.5×CH₂CHS); 49.2 (q,J=30 Hz, 0.5×CF₃CH); 49.5 (q, J=30 Hz, 0.5×CF₃CH); 51.8 (0.5×CHS); 52.1(0.5×CHS); 64.04 (0.5×CH₂CH₃); 64.2 (0.5×CH₂CH₃); 65.2 (0.5×CH₂CH₃);65.5 (0.5×CH₂CH₃); 70.4 (0.5×CH₂CH₃); 70.6 (0.5×CH₂CH₃); 100.9(0.5×CH(OEt)₂); 101.3 (0.5×CH(OEt)₂); 122.8 (q, J=283 Hz, 0.5×CF₃);123.0 (q, J=283 Hz, 0.5×CF₃); 158.3 (0.5×C(CH₃)₃); 158.4 (0.5×C(CH₃)₃);170.0 (0.5×C═O); 171.4 (0.5×C═O); 214.0 (0.5×C═S); 214.2 (0.5×C═S).

IR (ν, cm⁻¹) (CCl₄) 3440 (NH); 2973; 2910; 2810; 1732 (C═O); 1730 (C═O);1594; 1243; 1210; 1176; 1164; 1064.

Mass (IC, NH3) 420 (MH⁺-EtOH).

Conversions of the Adducts Having the Formula (IIA) Example 19N-[3-(2-oxo-pyrrolidin-1-yl)-1-trifluoromethyl-allyl] acetamide

C₁₀H₁₃F₃N₂O₂ M=250.22 g.mol⁻¹Reaction:

A solution of xanthate of example 12 (170 mg, 0.45 mmol) in 5 ml ofchlorobenzene is brought to reflux for 2 hours. The crude reactionproduct is brought to ambient temperature then concentrated at reducedpressure before being purified.

Purification:

Chromatography over silica gel (dichloromethane-methanol 98/2).

Product:

Pale yellow oil.

Yield:

Quantitative.

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 2.03 (s, 3H, COCH₃); 2.06-2.14 (m, 2H,CH₂CH₂CH₂); 2.46 (dd, J=7.3 Hz, 7.3 Hz, 2H, CH₂CO); 3.49 (dd, J=7.3 Hz,7.3 Hz, 2H, CH₂N); 4.87 (dd, J=14.7 Hz, 6.4 Hz, 1H, CH═CHN); 5.22 (qdd,J=9.4 Hz, 7.6 Hz, 6.4 Hz, 1H, CF₃CH); 7.20 (d, J=14.7 Hz, 1H, CH═CHN);7.43 (d, J=9.4 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 17.33 (CH₂CH₂CH₂); 22.82 (CH₃CO); 31.04(CH₂CO); 45.09 (CH₂N); 50.60 (q, J=30 Hz, CF₃CH); 101.48 (CH═CHN);124.53 (q, J=281 Hz, CF₃); 128.57 (CH═CHN); 170.28 (C═O); 173.84 (C═O).

IR (ν, cm⁻¹) (CCl₄) 3444 (NH); 2980; 1708 (C═O); 1667; 1558; 1497; 1400;1262; 1235; 1186; 1131.

Mass (IC, NH₃) 251 (MH⁺); 268 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 48.00 5.24 Actual(%) 47.62 5.31

Example 20N-[4-(1,3-dioxo-1,3-dihydro-isoindol-2-yl)-1-trifluoromethyl-butyl]acetamide

C₁₅H₁₅F₃N₂O₃ M=328.29 g.mol⁻¹Reaction:

LP is added, at a rate of 10 mol % (22 mg, 0.056 mmol) every hour, to asolution of the xanthate adduct of example 9 (250 mg, 0.56 mmol) in 4 mlpropan-2-ol, which solution has been degassed beforehand at reflux underargon. The reaction is stopped after 11 hours under reflux and theaddition of 110% of LP (244 mg, 0.61 mmol). The reaction medium is thenbrought to ambient temperature and concentrated at reduced pressurebefore being purified.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 4/6).

Product:

White crystalline.

Yield:

78%

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.48-1.60 (m, 1H, CF₃CH(NAc)CH₂);1.74-1.89 (m, 3H, CH₂CH₂N+CF₃CH(NAc)CH₂); 3.69 (t, J=6.8 Hz, 2H,CH₂CH₂N); 4.59-4.72 (m, 1H, CF₃CH); 6.40 (d, J=9.3 Hz, 1H, NH);7.69-7.71 (m, 2H, H_(Ar.)); 7.79-7.81 (m, 2H, H_(Ar.)).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 23.02 (CH₃CO); 24.72 (CH₂); 25.14(CH₂); 37.25 (CH₂N); 50.18 (q, J=30 Hz, CF₃CH); 123.35 (2×CH_(Ar.));125.05 (q, J=281 Hz, CF₃); 131.93 (Cq_(Ar.)); 134.19 (2×CH_(Ar.));168.48 (2×C═O_(Ar.)); 170.55 (C═O).

IR (ν, cm⁻¹)(CCl₄) 3445 (NH); 2932; 1774 (C═O); 1717 (C═O); 1505; 1438;1396; 1369; 1244; 1187; 1136.

MP (° C.) 179-180 (ethyl acetate-heptane)

Mass (IC, NH₃) 329 (MH⁺); 345 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 54.88 4.61 Actual(%) 54.84 4.58

Example 21 Ester of dithiocarbonic acidS-{1-[5-(1-acetylamino-2,2,2-trifluoro-ethyl)-2-oxo-[1,3]dioxolan-4-ylmethyl]-2,2-diethoxy-ethyl}O-ethyl ester

C17H₂₆F₃NO₇S₂ M=477.52 g.mol⁻¹Reaction:

Carried out according to the general operating method with 95 mg (0.27mmol) of xanthate of example 4 and 125 μl (0.82 mmol) of3,3-diethoxy-propene in 1 ml of 1,2-dichloroethane. The reaction isterminated after the addition of 5% of LP and 1 hour under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 3/7).

Product:

Pale yellow oil.

Yield:

40% (2 diastereoisomers at a ratio of 1/1), isolated with 17% of thedouble addition product:

¹HNMR (δ, ppm) b(CDCl₃, 400 MHz) 1.17 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.19(t, J=7.0 Hz, 3H, CH₂CH₃); 1.22 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.23 (t,J=7.0 Hz, 3H, CH₂CH₃); 1.42 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.43 (t, J=7.0Hz, 3H, CH₂CH₃); 1.95-2.15 (m, 2H, CH₂CHS); 2.07 (s, 3H, COCH₃); 2.09(s, 3H, COCH₃); 2.37-2.45 (m, 2H, CH₂CHS); 3.42-3.82 (m, 8H, CH₃CH₂);4.05-4.15 (m, 2H, CHS); 4.49-4.59 (m, 2H, CHOCO); 4.59 (s, 1H,CH(OEt)₂); 4.60 (s, 1H, CH(OEt)₂); 4.63 (q, J=7.0 Hz, 2H, CH₃CH₂); 4.64(q, J=7.0 Hz, 2H, CH₃CH₂); 4.77-4.89 (m, 1H, CHOCO); 4.97-5.09 (m, 3H,CF₃CH+CHOCO); 6.81 (d, J=9.4 Hz, 1H, NH); 6.83 (d, J=9.4 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.78 (2×CH₃CH₂); 15.15 (CH₃CH₂); 15.23(CH₃CH₂); 15.29 (2×CH₃CH₂); 22.70 (CH₃CO); 22.78 (CH₃CO); 33.22(CH₂CHS); 34.24 (CH₂CHS); 48.94 (CHS); 49.66 (CHS); 51.01 (q, J=31 Hz,CF₃CH); 51.08 (q, J=31 Hz, CF₃CH); 64.36 (CH₂CH₃); 64.47 (CH₂CH₃); 65.35(CH₂CH₃); 65.59 (CH₂CH₃); 70.75 (CH₂CH₃); 70.84 (CH₂CH₃); 76.37 (CHOCO);77.10 (CHOCO); 77.91 (CHOCO); 78.39 (CHOCO); 103.49 (CH(OEt)₂); 103.57(CH(OEt)₂); 123.58 (q, J=282 Hz, CF₃); 123.64 (q, J=283 Hz, CF₃); 153.34(OC═O); 153.46 (OC═O); 170.58 (NC═O); 170.70 (NC═O); 212.76 (C═S);213.04 (C═S).

Mass (IC, NH3) 433 (M-EtOH+H⁺); 496 (MNH₄ ⁺).

Example 22 N-(3,3-dimethoxy-1-trifluoromethyl-propyl)-acetamide

C₈H₁₄F₃NO₃ M=229.20 g.mol⁻¹Reaction:

A catalytic quantity of (±)-10-camphorsulphonic acid is added to asolution of xanthate of example 5 (200 mg, 0.57 mmol) in 10 ml ofmethanol. The whole is brought to reflux for 24 hours. The crudereaction product is then brought to ambient temperature thenconcentrated at reduced pressure before being purified.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 7/3).

Product:

Colourless crystalline.

Yield:

72% (10% of the aldehyde which corresponds to the unprotected product isalso isolated).

¹HNMR (δ, ppm)(CDCl₃, 400 MHz) 1.90 (ddd, J=14.4 Hz, 10.0 Hz, 4.0 Hz,1H, CH₂); 2.04 (ddd, J=14.4 Hz, 7.6 Hz, 3.3 Hz, 1H, CH₂); 2.02 (s, 3H,COCH₃); 3.31 (s, 3H, OCH₃); 3.33 (s, 3H, OCH₃); 4.43 (dd, J=7.6 Hz, 4.0Hz, 1H, CH(OMe)₂); 4.66-4.78 (m, 1H, CF₃CH); 6.66 (d, J=9.4 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 22.97 (CH₃CO); 31.69 (CH₂); 47.54 (q,J=31 Hz, CF₃CH); 53.29 (OCH₃); 53.88 (OCH₃); 101.55 (CH(OMe)₂); 125.09(q, J=281 Hz, CF₃); 170.46 (NC═O).

IR (ν, cm⁻¹) (CCl₄) 3444 (NH); 2936; 2833; 1704 (C═O); 1505; 1434; 1371;1285; 1248; 1188; 1138; 1065.

MP (° C.) 56-58 (ethyl acetate-heptane).

Mass (IC, NH₃) 198 (M-MeOH+H⁺); 230 (MH⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 41.92 6.16 Actual(%) 41.84 6.09

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 2.01 (s, 3H, COCH₃); 2.79-2.83 (m, 2H,CH₂); 5.08-5.21 (m, 1H, CF₃CH); 7.15 (d, J=9.4 Hz, 1H, NH); 9.68 (s, 1H,HC═O).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 22.76 (CH₃CO); 41.86 (CH₂); 458554 (q,J=33 Hz, CF₃CH); 124.76 (q, J=281 Hz, CF₃); 170.54 (NC═O); 197.18(HC═O).

Example 23N-[1-(5-bromo-1-methanesulphonyl-2,3-dihydro-1H-indol-3-ylmethyl)-2,2,2-trifluoro-ethyl]-acetamide

C₁₄H₁₆BrF₃N₂O₃S M=429.25 g.mol⁻¹Reaction:

LP is added, at a rate of 10 mol % (28 mg, 0.07 mmol) every hour, to asolution of the xanthate adduct of example 13 (396 mg, 0.72 mmol) in 4ml of 1,2-dichloroethane, which solution has been degassed beforehand atreflux under argon. The reaction is stopped after 11 hours under refluxand the addition of 110% of LP (314 mg, 0.790 mmol). The reaction mediumis then brought to ambient temperature and concentrated at reducedpressure before being purified.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 5/5).

Product:

White crystalline.

Yield:

90% (2 diastereoisomers at a ratio of 6/4)

First Diastereoisomer (Majority)

¹HNMR (δ, ppm) ((CD₃)₂CO, 400 MHz) 1.92-2.10 (m, 1H, CF₃CH(NAc)CH₂);1.97 (s, 3H, COCH₃); 2.18-2.24 (m, 1H, CF₃CH(NAc)CH₂); 3.01 (s, 3H,SO₂CH₃); 3.52-3.63 (m, 1H, NCH₂CH); 3.83 (d, J=10.3 Hz, 5.4 Hz, 1H,NCH₂); 4.15 (d, J=10.3 Hz, 10.0 Hz, 1H, NCH₂); 4.80-4.95 (m, 1H, CF₃CH);7.29 (d, J=8.6 Hz, 1H, H_(Ar)(HC═CNSO₂)); 7.41 (d, J=8.6 Hz, 1H,H_(Ar)(HC═CBr)); 7.66 (s, 1H, H_(Ar)(HC═CBr)); 7.76 (d, J=9.4 Hz, 1H,NH).

¹³CNMR (δ, ppm)(CD₃)₂CO, 400 MHz) 22.76 (CH₃CO); 33.25 (CF₃CH(NAc)CH₂);34.82 (NCH₂); 37.40 (CH₃SO₂); 49.28 (q, J=30 Hz, CF₃CH); 57.08 (NCH₂);115.83 (CH_(Ar.)); 116.26 (Cq_(Ar.)); 126.42 (q, J=281 Hz, CF₃); 129.51(CH_(Ar.)); 132.12 (CH_(Ar.)); 137.35 (Cq_(Ar.)); 142.52 (Cq_(Ar.));170.72 (C═O).

Second Diastereoisomer (Minority)

¹HNMR (δ, ppm) (CD₃)₂CO, 400 MHz) 1.96-2.07 (m, 1H, CF₃CH(NAc)CH₂); 2.03(s, 3H, COCH₃); 2.20-2.27 (m, 1H, CF₃CH(NAc)CH₂); 3.02 (s, 3H, SO₂CH₃);3.57-3.66 (m, 1H, NCH₂CH); 3.82 (d, J=10.0 Hz, 7.5 Hz, 1H, NCH₂); 4.11(d, J=10.0 Hz, 9.5 Hz, 1H, NCH₂); 4.74-4.87 (m, 1H, CF₃CH); 7.29 (d,J=8.5 Hz, 1H, H_(Ar)(HC═CNSO₂)); 7.40 (d, J=8.5 Hz, 1H, H_(Ar)(HC═CBr));7.41 (s, 1H, H_(Ar)(HC═CBr)); 7.67 (d, J=9.3 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CD₃)₂CO, 400 MHz) 22.77 (CH₃CO); 32.87 (CF₃CH(NAc)CH₂);34.70 (NCH₂); 36.71 (CH₃SO₂); 49.04 (q, J=30 Hz, CF₃CH); 56.42 (NCH₂);115.86 (CH_(Ar.)); 116.22 (Cq_(Ar.)); 126.50 (q, J=281 Hz, CF₃); 128.38(CH_(Ar.)); 131.99 (CH_(Ar.)); 137.83 (Cq_(Ar.)); 142.79 (Cq_(Ar.));170.87 (C═O).

Analyses on the Admixture of Diastereoisomers

IR (ν, cm⁻¹) (nujol) 3285 (NH); 1759 (C═O); 1549; 1352; 1307; 1269;1214; 1161; 1128; 1112.

Mass (IC, NH₃) 430 (MH⁺); 447 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 39.17 3.76 Actual(%) 38.73 3.69

Example 24 Ester ofS-{2-[5-(1-acetylamino-2,2,2-trifluoro-ethyl)-2-oxo-[1,3]dioxolan-4-yl]-1-trimethylsilanylmethyl-ethyl}dithiocarbonic acid O-ethyl ester

C₁₆H₂₆F₃NO₅S₂Si M=461.59 g.mol⁻¹Reaction:

Carried out according to the general operating method with 130 mg (0.37mmol) of xanthate of example 4 and 178 μl (1.12 mmol) ofallyl-trimethyl-silane in 1 ml of 1,2-dichloroethane. The reaction isterminated after the addition of 5% of LP and 45 minutes under reflux.

Purification:

Chromatography over silica gel (ether-petroleum ether 3/7).

Product:

Pale yellow oil.

Yield:

72% (2 diastereoisomers at a ratio of 1/1)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 0.07 (s, 9H, (CH₃)₃Si); 0.08 (s, 9H,(CH₃)₃Si); 0.96-1.15 (m, 4H, CH₂Si(CH₃)₃); 1.41 (t, J=7.0 Hz, 3H,CH₂CH₃); 1.42 (t, J=7.0 Hz, 3H, CH₂CH₃); 2.12 (s, 6H, 2×COCH₃);2.14-2.35 (m, 4H, 2×OCHCH₂CHS); 3.83-3.90 (m, 1H, CHS); 3.90-3.97 (m,1H, CHS); 4.54-4.62 (m, 2H, 2×CHSCH₂CHO); 4.63 (q, J=7.0 Hz, 2H,CH₃CH₂); 4.64 (q, J=7.0 Hz, 2H, CH₃CH₂); 4.75 (d, 1H, J=5.8 Hz, 1H,CF₃CHCH(NAc)CHO); 4.84 (d, 1H, J=6.58 Hz, 1H, CF₃CHCH(NAc)CHO);4.93-5.04 (m, 2H, CF₃CH); 7.45 (d, J=10.5 Hz, 1H, NH); 7.47 (d, J=10.5Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) −0.79 to −0.65 (m, (CH₃)₃Si); 13.81(2×CH₃CH₂); 20.99 (OCHCH₂CHS); 22.57 (2×CH₃CO); 22.92 (OCHCH₂CHS); 41.29(CH₂Si); 42.12 (CH₂Si); 43.72 (CHS); 44.33 (CHS); 50.70 (q, J=32 Hz,2×CF₃CH); 70.25 (CH₂CH₃); 70.29 (CH₂CH₃); 76.75 (CHOC═O); 77.19(CHOC═O);77.83 (CHOC═O); 77.99 (CHOC═O); 123.45 (q, J=283 Hz, 2×CF₃);154.02 (OC═O); 154.13 (OC═O); 171.66 (NC═O); 171.83 (NC═O); 213.11(C═S); 213.22 (C═S).

IR (ν, cm⁻¹) (CCl₄) 3435 (NH); 3328 (NH); 2954; 1807 (C═O); 1697 (C═O);1502; 1371; 1301; 1277; 1251; 1221; 1189; 1142; 1111; 1050.

Mass (IC, NH₃) 340 (M-HSCSOEt+H⁺); 463 (MH⁺); 480 (MNH₄ ⁺).

Example 25N-[1-(5-ethoxy-2-oxo-[1,3]dithiolan-4-ylmethyl)-2,2,2-trifluoro-ethyl]-acetamide

C₁₀H₁₄F₃NO₃S₂ M=317.35 g.mol⁻¹Reaction:

4 drops of concentrated sulphuric acid are added to a solution ofxanthate adduct of example 8 in 10 ml of methanol. After 48 hours atambient temperature, the methanol is evaporated at reduced pressure andthe residue is placed in dichloromethane. A saturated solution of sodiumhydrogen carbonate is added and the organic phase is separated. Afterdrying over magnesium sulphate, filtration and concentration in avacuum, the organic residue is then purified.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 3/7).

Product:

Pale yellow oil.

Yield:

21%

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.24 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.27 (t,J=7.0 Hz, 3H, CH₂CH₃); 2.02-2.08 (m, 2H, CF₃CH(NAc)CH₂); 2.07 (s, 3H,COCH₃); 2.08 (s, 3H, COCH₃); 2.45 (ddd, 1H, J=14.6 Hz, 8.2 Hz, 4.1 Hz,1H, CF₃CH(NAc)CH₂); 2.57 (ddd, 1H, J=14.6 Hz, 10.0 Hz, 2.9 Hz, 1H,CF₃CH(NAc)CH₂); 3.44-3.54 (m, 2H, CH₂CH₃); 3.70-3.84 (m, 2H, CH₂CH₃);4.03-4.07 (m, 1H, CH₂CHS); 4.30-4.75 (m, 1H, CH₂CHS); 4.67-4.88 (m, 2H,CF₃CH); 5.52 (d, J=1.9 Hz, 1H, SCH(OEt)); 5.60 (d, J=3.5 Hz, 1H,SCH(OEt)); 6.59 (d, J=10.0 Hz, 1H, NH); 6.63 (d, J=9.4 Hz, 1H, NH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 14.45 (CH₂CH₃); 14.66 (CH₂CH₃); 22.97(CH₃CO); 23.07 (CH₃CO); 28.25 (CH₂CHS); 33.31 (CH₂CHS); 47.95 (q, J=30Hz, CF₃CH); 48.87 (q, J=30 Hz, CF₃CH); 53.21 (CH₂CHS); 54.49 (CH₂CHS);65.68 (CH₂CH₃); 65.92 (CH₂CH₃); 90.58 (SCH(OEt)); 94.07 (SCH(OEt));123.51 (q, J=282 Hz, CF₃); 123.58 (q, J=282 Hz, CF₃); 170.85 (NC═O);171.14 (NC═O); 195.48 (SC═O); 195.67 (SC═O).

IR (ν, cm⁻¹) (CCl₄) 3439 (NH); 2981; 1701 (C═O); 1666 (C═O); 1549; 1500;1239; 1192; 1144.

Mass (IC, NH₃) 272 (M-EtOH+H⁺); 318 (MH⁺); 335 (MNH₄ ⁺).

Example 26 4-benzoylamino-5,5-5-trifluoro-butyl ester of acetic acid

C₁₄H₁₆F₃NO₃ M=303.11 g.mol⁻¹Reaction:

LP is added, at a rate of 10% (52 mg, 0.13 mmol) every hour, to asolution of xanthate adduct of example 15 (551 mg, 1.30 mmol) inpropan-2-ol (8 ml), which solution has been degassed beforehand atreflux under argon. The reaction is stopped after 11 hours under refluxand the addition of 120% of LP (6.2 g, 15.5 mmol). The reaction mediumis then brought to ambient temperature and concentrated at reducedpressure before being purified.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 1/9).

Product:

Translucent crystals.

Yield:

62%

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.6 (quin, J=7.2 Hz, 2H, CH₂CH₂CH₂);2.01 (s, 3H, COCH₃); 2.23 (t, J=8.3 Hz, 2H, CF₃CHNCH₂); 4.05 (t, J=8.8Hz, 2H, CH₂OCOCH3); 4.85 (m, 1H, CF₃CH); 6.34 (d, J=8.9 Hz, 1H, NH);7.41-7.92 (m, 5H, CH_(Ar.)).

NMR¹³C (δ, ppm) (CDCl₃, 100 MHz) 22.8 (CH₃CO); 28.4 (q, J=30 Hz, CF₃CH);33.2 (CF₃CHNCH₂); 31.8 (CF₃CHNCH₂); 63.7 (CH₂OCOCH₃); 124.7 (q, J=281Hz, CF₃); 128.5 (2×CH_(Ar.)); 128.9 (2×CH_(Ar.)); 129.2 (CH_(Ar.));132.4 (Cq_(Ar.)); 179.6 (C═O); 180.0 (C═O).

IR (ν, cm⁻¹) (CCl₄) 3451 (NH); 2926; 2881; 1710 (C═O); 1688 (C═O); 1510;1486; 1455; 1367; 1236; 1187; 1147; 1072.

Mass (IC, NH3) 304 (MH⁺); 321 (MNH₄ ⁺).

Microanalysis Element Carbon Hydrogen Calculated (%) 55.44 5.32 Actual(%) 55.27 5.18

MP 49° C. (ether)

Examples of the Method for Preparing Compounds Having the Formula(VIIIA) Example 27N-(2-acetylamino-3,3,3-trifluoro-1-trifluoromethyl-propyl)-acetamide

C₈H₁₀F₆N₂O₂ M=280.17 g.mol⁻¹Reaction:

LP is added, at a rate of 10 mol % (80 mg, 0.2 mmol) every 10 minutes,to a solution of xanthate of example 1 (522 mg, 2 mmol) in 16 ml ofchlorobenzene, which solution has been degassed beforehand at refluxunder argon. The reaction is stopped after 2 hours under reflux and theaddition of 120% of LP (960 mg, 2.4 mmol). The reaction medium is thenbrought to ambient temperature and concentrated at reduced pressurebefore being purified.

Purification:

By means of precipitation in an admixture of ether-petroleum ether 1/9.

Product:

Colourless solid.

Yield:

79% (2 diastereoisomers at a ratio of 7/5)

First Diastereoisomer (Majority)

¹HNMR (δ, ppm) ((CD₃)₂SO, 400 MHz) 1.90 (s, 6H, CH₃CO); 4.90-5.03 (m,2H, CF₃CH); 8.86 (d, J=8.7 Hz, 2H, NH).

¹³CNMR (δ, ppm) ((CD₃)₂SO, 400 MHz) 22.21 (2×CH₃CO); 47.77 (q, J=29 Hz,2×CF₃CH); 124.01 (q, J=282 Hz, 2×CF₃); 169.61 (2×NC═O).

Second Diastereoisomer (Minority)

NMR¹H (δ, ppm) ((CD₃)₂SO, 400 MHz) 1.98 (s, 6H, CH₃CO); 5.17 (qd, J=8.2Hz, 9.2 Hz, 2H, CF₃CH); 8.41 (d, J=9.2 Hz, 2H, NH).

¹³CNMR (δ, ppm) ((CD₃)₂SO, 400 MHz) 22.40 (2×CH₃CO); 47.19 (q, J=29 Hz,2×CF₃CH); 123.89 (q, J=282 Hz, 2×CF₃); 169.54 (2×NC═O).

Analyses on the Admixture of Diastereoisomers

IR (ν, cm⁻¹) (nujol) 3284 (NH); 3072; 1674 (C═O); 1547; 1340; 1301;1255; 1238; 1181; 1153; 1108.

Mass (IC, NH₃) 281 (MH⁺); 298 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 34.30 3.60 Actual(%) 33.67 3.63

Example of the Method for Preparing Compounds Having the Formula (I_(B))Synthesis of Xanthate 2-Trifluoromethylethanol Example 28 O-ethyl andS-(1-hydroxy-2,2,2-trifluoro-ethyl) ester of dithiocarbonic acid

C₅H₇F₃O₂S₂ M=220.23 g.mol⁻¹Reaction:

The salt of potassium ethylxanthogenate (737 mg, 4.62 mmol) is added toa solution of 2,2,2-trifluoro-1-methoxy-ethanol (300 mg, 2.31 mmol) inacetone (5 ml). The reaction admixture is cooled to 0° C. and sulphuricacid (123.6 μL, 2.31 mmol) is added drop by drop. After 1 hour at 0° C.,the reaction admixture is concentrated at reduced pressure. The residueis placed in ether, filtered and concentrated again at reduced pressure.

Product:

Yellow oil.

Yield:

69%

NMR¹H (δ, ppm)(CDCl₃, 400 MHz) 1.54 (t, J=6.3 Hz, 3H, CH₂CH₃); 4.71 (q,J=6.3 Hz, 2H, CH₃CH₂); 6.02 (q, J=5.7 Hz, 1H, CF₃CH).

NMR¹³C (δ, ppm)(CDCl₃, 100 MHz) 13.7 (CH₃CH₂); 57.8 (q, J=30 Hz, CF₃CH);71.4 (CH₂CH₃); 124.4 (q, J=280 Hz, CF₃); 207.1 (C═S).

IR (ν, cm⁻¹)(CCl₄) 2961; 1453; 1314; 1231; 1130; 1052; 1023.

Mass (IC, NH3) 221 (MH⁺), 238 (MNH₄ ⁺).

Example 29 O-ethyl and S-(1-acetyl-2,2,2-trifluoro-ethyl) ester ofdithiocarbonic acid

C₇H₉F₃O₃S₂ M=262.27 g.mol⁻¹Reaction:

The salt of potassium ethylxanthogenate (4.61 g, 46.2 mmol) is added toa solution of 2,2,2-trifluoro-1-methoxy-ethanol (3 g, 23.1 mmol) inacetone (15 ml). The reaction admixture is cooled to 0° C. and sulphuricacid (1.24 ml, 23.1 mmol) is added drop by drop. After 1 hour at 0° C.,the reaction admixture is concentrated at reduced pressure. The residueis placed in ether, filtered and concentrated again at reduced pressure.

The residue is placed in acetone (5 ml), cooled to 0° C. Sulphuric acid(1.24 ml, 23.1 mmol), then acetic anhydride (21.7 ml, 231 mmol) areadded drop by drop.

After one hour at 0° C., the reaction admixture is concentrated atreduced pressure, placed in ether, washed in water and then with anaqueous solution saturated with potassium carbonate, dried andconcentrated again at reduced pressure.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 1/9)

Product:

Yellow oil.

Yield:

60%

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.48 (t, J=5.8 Hz, 3H, CH₂CH₃); 2.21 (s,3H, COCH₃); 4.71 (q, J=5.8 Hz, 2H, CH₃CH₂); 7.32 (q, J=6.0 Hz, 1H,CF₃CH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 12.5 (CH₃CH₂); 21.0 (COCH₃); 57.6 (q,J=38 Hz, CF₃CH); 70.4 (CH₂CH₃); 123.0 (q, J=280 Hz, CF₃); 179.5 (C═O);206.9 (C═S).

IR (ν, cm⁻¹) (CCl₄) 2986; 2939; 1778 (C═O); 1442; 1370; 1344; 1194;1131; 1032; 868; 823.

Mass (IC, NH3) 262 (MH⁺), 279 (MNH₄ ⁺).

Example 30 1-ethoxythiocarbonylsulphanyl-2,2,2-trifluoro-ethyl ester ofbenzoic acid

C₁₂H₁₁F₃O₃S₂ M=324.34 g.mol⁻¹Reaction:

The salt of potassium ethylxanthogenate (4.61 g, 46.2 mmol) is added toa solution of 2,2,2-trifluoro-1-methoxy-ethanol (3 g, 23.1 mmol) inacetone (15 ml). The reaction admixture is cooled to 0° C. and sulphuricacid (1.24 ml, 23.1 mmol) is added drop by drop. After one hour at 0°C., the reaction admixture is concentrated at reduced pressure. Theresidue is placed in ether, washed in water, then with an aqueoussolution saturated with potassium carbonate, dried and concentratedagain at reduced pressure.

This residue is then placed in dichloromethane (5 ml) and cooled to 0°C. Benzoic anhydride (6.27 g, 27.7 mmol), DMAP (4-dimethylaminopyridine)(845 mg, 6.93 mmol), and triethylamine (5.51 ml, 39.3 mmol) are addeddrop by drop.

After 3 hours at 0° C., the reaction admixture is concentrated atreduced pressure, placed in dichloromethane, washed in water and thenwith an aqueous solution saturated with ammonium chloride, dried andconcentrated again at reduced pressure.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 5/95)

Product:

Dark yellow oil.

Yield:

58%

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.30 (t, J=6.2 Hz, 3H, CH₂CH₃);3.86-3.91 (m, 1H, CH₃CH₂); 3.96-4.01 (m, 1H, CH₃CH₂); 6.28 (q, J=4.0 Hz,1H, CF₃CH); 7.50 (t, J=8.0 Hz, 2H_(Ar), CH_(Ar)═CH_(Ar)═CH_(Ar)C_(qAr));7.65 (t, J=7.6 Hz, 1H_(Ar), CH_(Ar)═CH_(Ar)═CH_(Ar)C_(qAr)); 8.13 (t,2H_(Ar), J=7.2 Hz, CH_(Ar)═CH_(Ar)═CH_(Ar)C_(qAr)).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 14.3 (CH₃CH₂); 68.5 (CH₂CH₃); 90.0 (q,J=39 Hz, CF₃CH); 120.0 (q, J=279 Hz, CF₃); 127.3 (2×CH_(Ar)); 128.2(2×CH_(Ar)); 129.8 (CH_(Ar)); 133.5 (C_(qAr)); 164.3 (C═O); 214.1 (C═S).

IR (ν, cm⁻¹) (CCl₄) 2984; 2929; 1739 (C═O); 1601; 1452; 1290; 1262;1193; 1169 (C═S); 1113; 1078; 1062; 1025; 988.

Mass (IC, NH3) 325 (MH⁺), 342 (MNH₄ ⁺).

Radical Additions Examples of the Method for Preparing Compounds Havingthe Formula (IIB) Example 31 O-ethyl andS-[3-acetoxy-1-(1,3-dioxo-1,3-dihydro-isoindol-2-ylmethyl)-4,4,4-trifluoro-butyl]diester of dithiocarbonic acid

C₁₈H₁₈F₃NO₅S₂ M=449.47 g.mol⁻¹Reaction:

Carried out according to the general operating method with 337 mg (1.29mmol) of xanthate of example 29 and 481 mg (2.57 mmol) of allylphthalimide in 1,2-dichloroethane (3 ml). The reaction is terminatedafter the addition of 15% of LP (26 mg) and 4 hours 30 minutes underreflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 1/9 then2/8).

Product:

Pale yellow oil.

Yield:

78% (admixture of 2 diastereoisomers at a ratio of 1/1)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.22 (2t, J=7.0 Hz, 3H, CH₂CH₃);1.38-1.42 (m, 2H, CF₃CH(OAc)CH₂); 2.18 (s, 1.5H, COCH₃); 2.22 (s, 1.5H,COCH₃); 3.98-4.02 (m, 2H, CH₂N); 4.21-4.24 (m, 0.5H, CHS); 4.52 (q,J=7.0 Hz, 1H, CH₃CH₂); 4.54 (q, J=7.0 Hz, 1H, CH₃CH₂); 4.54-4.57 (m,0.5H, CHS); 5.63-5.66 (m, 1H, CF₃CH); 7.70-7.73 (m, 2H,H_(Ar.)(C_(q)CH═CH)); 7.79-7.84 (m, 2H, H_(Ar.)(C_(q)CH═CH)).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 12.2 (0.5×CH₃CH₂); 12.3 (0.5×CH₃CH₂);20.0 (0.5×CH₃CO); 21, (0.5×CH₃CO); 30.2 (0.5×CF₃CH(OAc)CH₂); 30.4(0.5×CF₃CH(OAc)CH₂); 39.8 (0.5×CH₂N); 40.2 (0.5×CH₂N); 43.8 (0.5×CHS);44.1 (0.5×CHS); 63.5 (q, J=35 Hz, 0.5×CF₃CH); 63.7 (q, J=35 Hz,0.5×CF₃CH); 69.9 (0.5×CH₂CH₃); 69.9 (0.5×CH₂CH₃); 121.6(CH_(Ar.)(C_(q)CH═CH)); 121.6 (CH_(Ar.)(C_(q)CH═CH)); 124.6 (q, J=272Hz, 0.5×CF₃); 124.9 (q, J=280 Hz, 0.5×CF₃); 130.8 (Cq_(Ar.)); 132.2(Cq_(Ar.)); 165.3 (2×CH_(Ar.)(C_(q)CH═CH)); 167.0 (C═O_(Ar.)); 167.0(C═O_(Ar.)); 168.0 (0.5×C═O); 168.0 (0.5×C═O); 212.0 (0.5×C═S); 212.5(0.5×C═S).

IR (ν, cm⁻¹) (CCl₄) 2982; 2928; 1766 (C═O); 1723 (C═O); 1615; 1468;1430; 1392; 1371; 1283; 1213; 1146; 1112; 1049.

Mass (IC, NH3) 450 (MH⁺); 467 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 48.10 4.04 Actual(%) 48.06 4.09

Example 32 O-ethyl andS-(3-acetoxy-4,4,4-trifluoro-1-trimethyl-silanylmethyl-butyl) ester ofdithiocarbonic acid

C₁₃H₂₃F₃NO₃S₂Si M=376.54 g.mol⁻¹Reaction:

Carried out according to the general operating method with 300 mg (1.14mmol) of xanthate of example 29 and 392 mg (3.43 mmol) ofallyltrimethylsilane in 1,2-dichloroethane (4 ml). The reaction isterminated after the addition of 5% of LP (22 mg) and 1 hour 45 minutesunder reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 1/9 then2/8).

Product:

White crystals.

Yield:

80% (admixture of 2 diastereoisomers at a ratio of 2/3)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 0.08 (s, 3.6H, Si(CH₃)₃); 0.09 (s, 5.4H,Si(CH₃)₃); 0.83-1.15 (m, 2H, CH₂Si(CH₃)₃); 1.42 (t, J=6.4 Hz, 3H,CH₂CH₃); 2.03-2.26 (m, 2H, CF₃CH(OAc)CH₂); 2.15 (s, 1.2H, COCH₃); 2.17(s, 1.8H, COCH₃); 3.72 (m, 0.4H, CHS); 3.95 (m, 0.6H, CHS); 4.65 (q,J=6.4 Hz, 2H, CH₃CH₂); 5.39-5.45 (m, 0.4H, CF₃CH); 5.48-5.52 (m, 0.6H,CF₃CH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) −0.7 (1.2×Si(CH₃)₃); −0.7(1.8×Si(CH₃)₃); 13.8 (0.4×CH₃CH₂); 13.8 (0.6×CH₃CH₂); 19.7(0.4×CH₂OAcCHCF₃); 19.8 (0.6×CH₂OAcCHCF₃); 22.1 (0.4×CH₃CO); 22.5(0.6×CH₃CO); 34.9 (0.4×CH₂SiMe₃); 35.2 (0.6×CH₂SiMe₃); 43.4 (0.4×CHS);43.7 (0.6×CHS); 68.1 (q, J=32 Hz, 0.4×CF₃CH); 68.2 (q, J=32 Hz,0.6×CF₃CH); 70.3 (0.4×CH₂CH₃); 70.5 (0.6×CH₂CH₃); 122.3 (q, J=281 Hz,0.4×CF₃); 125.4 (q, J=281 Hz, 0.6×CF₃); 170.1 (0.4×C═O); 170.3(0.6×C═O); 212.1 (0.4×C═S); 213.2 (0.6×C═S).

IR (ν, cm⁻¹)(CCl₄) 2956; 2927; 2855; 2355; 1764 (C═O); 1441; 1371; 1285;1268; 1214; 1182; 1140; 1112; 979; 938.

Mass (IC, NH3) 377 (MH⁺); 394 (MNH₄ ⁺).

MP 120° C. (ether)

Example 33 3-acetoxy-1-ethoxythiocarbonylsulphanyl-4,4,4-trifluoro-butylester of acetic acid

C₁₁H₁₅F₃O₅S₂ M=348.36 g.mol⁻¹Reaction: Carried out according to the general operating method with 200mg (0.77 mmol) of xanthate of example 29 and 77 μL (0.92 mmol) of vinylacetate in 1,2-dichloroethane (1.5 ml). The reaction is terminated afterthe addition of 5% of LP (15 mg) and 1 hour 30 minutes under reflux.Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 1/9).

Product:

Thick pale yellow oil.

Yield:

79% (admixture of 2 diastereoisomers at a ratio of 1/1)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.48 (t, J=6.7 Hz, 1.5H, CH₂CH₃); 1.49(t, J=6.7 Hz, 1.5H, CH₂CH₃); 2.12 (s, 3H, COCH₃); 2.23 (s, 3H, COCH₃);2.39-2.46 (m, 1H, CF₃CH(OAc)CH₂); 2.49-2.52 (m, 1H, CF₃CH(OAc)CH₂); 4.60(q, J=6.7 Hz, 1H, CH₃CH₂); 4.61 (q, J=6.7 Hz, 1H, CH₃CH₂); 5.43-5.48 (m,0.5H, CF₃CH); 5.49-5.52 (m, 0.5H, CF₃CH); 6.68-6.73 (m, 0.5H, CHS);6.79-6.84 (m, 0.5H, CHS).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.4 (0.5×CH₃CH₂); 13.6 (0.5×CH₃CH₂);20.8 (0.5×CH₃CO); 20.9 (0.5×CH₃CO); 22.9 (0.5×CH₃CO); 23.1 (0.5×CH₃CO);33.1 (0.5×CH₂CHS); 33.5 (0.5×CH₂CHS); 47.6 (q, J=32 Hz, 0.5×CF₃CH); 47.8(q, J=32 Hz, 0.5×CF₃CH); 70.5 (0.5×CH₂CH₃); 70.7 (0.5×CH₂CH₃); 77.2(0.5×CHS); 77.9 (0.5×CHS); 125.2 (q, J=281 Hz, 0.5×CF₃); 125.7 (q, J=281Hz, 0.5×CF₃); 168.9 (0.5×OC═O); 169.8 (0.5×OC═O); 170.6 (0.5×C═O); 170.8(0.5×C═O); 209.2 (0.5×C═S); 209.7 (0.5×C═S).

IR (ν, cm⁻¹) (CCl₄) 3511; 2983; 2938; 2869; 2412; 1764 (C═O); 1720(C═O); 1641; 1430; 1398; 1371; 1284; 1228; 1146; 1111; 1086; 1048; 1016.

Mass (IC, NH3) 289 (M H⁺—AcOH); 349 (MH⁺); 366 (MNH₄ ⁺).

Example 34 O-ethyl andS-(3-acetoxy-1-diethoxymethyl-4,4,4-trifluoro-pentyl) diester ofdithiocarbonic acid

C₁₅H₂₅F₃O₅S₂ M=406.49 g.mol⁻¹Reaction:

Carried out according to the general operating method with 200 mg (0.76mmol) of xanthate of example 29 and 220 mg (1.5 mmol) of4,4-diethoxy-butene in 1,2-dichloroethane (2 ml). The reaction isterminated after the addition of 5% of LP (15 mg) and 1 hour 30 minutesunder reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 1/9).

Product:

Thick pale yellow oil.

Yield:

82% (admixture of 2 diastereoisomers at a ratio of 1/1)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.20 (t, J=7.0 Hz, 6H, CH(OCH₂CH₃)₂);1.25 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.42 (dd, J₁=7.5 Hz, J₂=9.1 Hz, 2H,CH—CH₂—CH(OCH₂CH₃)₂); 2.25-2.28 (m, 2H, CF₃CH(OAc)CH₂); 3.51-3.55 (m,2H, CH₃CH₂O); 3.59-3.65 (m, 2H, CH₃CH₂O); 4.62-4.67 (m, 2H, CH₃CH₂O);5.05 (dd, J₁=9.2 Hz, J₂=12.0 Hz, 0.5H, CH(OEt)₂); 5.12 (dd, J₁=9.2 Hz,J₂=12.0 Hz, 0.5H, CH(OEt)₂); 5.47-5.52 (m, 0.5H, CHS); 5.61-5.64 (m,0.5H, CHS); 5.89-5.93 (m, 1H, CF₃CH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.9 (CH₃CH₂); 14.5 (CH₃CH₂); 16.2(0.5×CH₃CH₂); 17.2 (0.5×CH₃CH₂); 21.0 (0.5×CH—CH₂—CH(OCH₂CH₃)₂)); 21.2(0.5×CH—CH₂—CH(OCH₂CH₃)₂)); 24.3 (0.5×CH₃CO); 24.5 (0.5×CH₃CO); 30.2(0.5×CF₃CH(OAc)CH₂); 30.6 (0.5×CF₃CH(OAc)CH₂); 43.1 (q, J=30 Hz,0.5×CF₃CH); 43.5 (q, J=30 Hz, 0.5×CF₃CH); 51.2 (0.5×CHS); 51.5(0.5×CHS); 61.8 (0.5×CH₂CH₃); 62.1 (0.5×CH₂CH₃); 64.0 (0.5×CH₂CH₃); 64.2(0.5×CH₂CH₃); 69.7 (0.5×CH₂CH₃); 69.8 (0.5×CH₂CH₃); 100.9(0.5×CH(OEt)₂); 101.3 (0.5×CH(OEt)₂); 122.9 (q, J=283 Hz, 0.5×CF₃);123.1 (q, J=283 Hz, 0.5×CF₃); 158.3 (0.5×C═O); 158.6 (0.5×C═O); 214.1(0.5×C═S); 214.4 (0.5×C═S).

IR (ν, cm⁻¹)(CCl₄) 2978; 2928; 2336; 1764 (C═O); 1442; 1372; 1283; 1215;1182; 1142; 1112; 1052.

Mass (IC, NH3) 363 (MH+-EtOH).

Example 35 O-ethyl and S-(3-acetoxy-1-cyanomethyl-4,4,4-trifluoro)butylester of dithiocarbonic acid

C₁₁H₁₄F₃NO₃S₂ M=329.36 g.mol⁻¹Reaction:

Carried out according to the general operating method with 200 mg (0.77mmol) of xanthate of example 29 and 109 μL (2.31 mmol) ofbut-3-enenitrile in 1,2-dichloroethane (2 ml). The reaction isterminated after the addition of 10% of LP (31 mg) and 3 hours underreflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 5/95).

Product:

Thick pale yellow oil.

Yield:

92% (admixture of 2 diastereoisomers at a ratio of 3/2)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.41 (t, J=7.0 Hz, 1.8H, CH₂CH₃); 1.46(t, J=7.0 Hz, 1.2H, CH₂CH₃); 2.15 (s, 1.8H, COCH₃); 2.21 (s, 1.2H,COCH₃); 2.08-2.31 (m, 2H, CF₃CH(OAc)CH₂); 2.82-3.07 (m, 2H, CH₂CN);3.90-3.95 (m, 0.6H, CHS); 4.03-4.07 (m, 0.4H, CHS); 4.61 (q, J=7.0 Hz,1.2H, CH₃CH₂); 4.63 (q, J=7.0 Hz, 0.8H, CH₃CH₂); 5.41-5.45 (m, 0.6H,CF₃CH); 5.57-5.60 (m, 0.4H, CF₃CH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.7 (CH₃CH₂); 20.1(0.6×CF₃CH(OAc)CH₂); 22.3 (CH₃CO); 24.2 (0.4×CF₃CH(OAc)CH₂); 30.8(0.6×CH₂CN); 31.5 (0.4×CH₂CN); 42.0 (0.6×CHS); 42.4 (0.4×CHS); 66.4 (q,J=30 Hz, 0.6×CF₃CH); 66.7 (q, J=30 Hz, 0.4×CF₃CH); 70.6 (0.6×CH₂CH₃);70.9 (0.4×CH₂CH₃); 115.9 (0.6×CN); 116.1 (0.4×CN); 121.6 (q, J=281 Hz,0.6×CF₃); 124.9 (q, J=281 Hz, 0.4×CF₃); 168.5 (0.6×C═O); 169.1(0.4×C═O); 210.5 (0.6×C═S); 210.9 (0.4×C═S).

IR (ν, cm⁻¹)(CCl₄) 2928; 1764 (C═O); 1372; 1279; 1210; 1186; 1111; 1083;1049; 1006; 969.

Mass (IC, NH3) 330 (MH⁺); 347 (MNH₄ ⁺).

Example 36 O-ethyl andS-1-(2-acetoxy-3,3,3-trifluoro-propyl)-4-oxo-pentyl diester ofdithiocarbonic acid

C₁₃H₁₉F₃O₄S₂ M=360.42 g.mol⁻¹Reaction:

Carried out according to the general operating method with 200 mg (0.76mmol) of xanthate according to example 29 and 225 mg (2.28 mmol) ofhex-5-en-2-one in 1,2-dichloroethane (2 ml). The reaction is terminatedafter the addition of 10% of LP (30 mg) and 3 hours under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 5/95).

Product:

Pale yellow oil.

Yield

88% (admixture of 2 diastereoisomers at a ratio of 3/2)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.42 (t, J=7.0 Hz, 1.8H, CH₂CH₃); 1.47(t, J=7.0 Hz, 1.2H, CH₂CH₃); 1.69-1.74 (m, 1.2H, CH₂COCH₃); 1.78-1.82(m, 0.8H, CH₂COCH₃); 1.98 (s, 1.8H, COCH₃); 2.10 (s, 1.8H, COCH₃); 2.11(s, 1.2H, COCH₃); 2.12 (s, 1.2H, COCH₃); 2.02-2.31 (m, 2H, CH₂CH₂COCH₃);2.51-2.70 (m, 2H, CH₂CHS); 3.68-3.74 (m, 0.6H, CHS); 3.91-3.95 (m, 0.4H,CHS); 4.58 (q, J=7.0 Hz, 1.2H, CH₃CH₂); 4.64 (q, J=7.0 Hz, 0.8H,CH₃CH₂); 5.39-5.51 (m, 0.6H, CF₃CH); 5.49-5.54 (m, 0.4H, CF₃CH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.3 (CH₃CH₂); 20.3 (CH₃CO); 24.4(0.6×CH₂COCH₃); 25.7 (0.4×CH₂COCH₃); 29.6 (0.6×CH₃CO); 31.5 (0.4×CH₃CO);32.5 (0.6×CH₂CH₂COCH₃); 33.5 (0.4×CH₂CH₂COCH₃); 39.8 (0.6×CH₂CHS); 40.0(0.4×CH₂CHS); 45.9 (0.6×CHS); 46.4 (0.4×CHS); 66.7 (q, J=32 Hz,0.6×CF₃CH); 67.0 (q, J=30 Hz, 0.4×CF₃CH); 69.9 (0.6×CH₂CH₃); 70.3(0.4×CH₂CH₃); 124.5 (q, J=281 Hz, 0.6×CF₃); 124.6 (q, J=281 Hz,0.4×CF₃); 168.6 (0.6×OC═O); 169.2 (0.4×OC═O); 206.7 (0.6×C═O); 206.9(0.4×C═O); 212.4 (0.6×C═S); 213.2 (0.4×C═S).

IR (ν, cm⁻¹)(CCl₄) 2983; 2926; 2335; 1764 (OC═O); 1721 (NC═O); 1441;1371; 1283; 1214; 1182; 1141; 1053; 909.

Mass (IC, NH3) 361 (MH⁺), 378 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 44.91 5.65 Actual(%) 44.91 5.66

Example 374-[4-bromo-phenyl)-methanesulphonyl-amino]-3-ethoxycarbonyl-sulphanyl-1-trifluoromethyl-butyl]ester of acetic acid

C₁₇H₂₁BrF₃NO₃S₃ M=552.42 g.mol⁻¹Reaction:

Carried out according to the general operating method with 1.54 g (5.88mmol) of xanthate of example 29 and 2.55 mg (8.88 mmol) ofN-allyl-N-(4-bromophenyl)-methanesulphonamide in 1,2-dichloroethane (8ml). The reaction is terminated after the addition of 20% of LP (468 mg)and 8 hours under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 1/9).

Product:

Pale yellow oil.

Yield:

71% (2 diastereoisomers at a ratio of 1/1)

First Diastereoisomer

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.28 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.96 (s,3H, COCH₃); 2.29-2.35 (m, 2H, CF₃CH(OAc)CH₂); 2.93 (s, 3H, SO₂CH₃);3.67-3.73 (m, 1H, CHS); 3.94-3.99 (m, 2H, CH₂N); 4.31 (q, J=7.0 Hz 2H,CH₃CH₂); 4.59-4.64 (m, 1H, CF₃CH); 7.23 (d, J=8.0 Hz, 2H,H_(Ar)(HC═CNSO₂)); 7.53 (d, J=8.0 Hz, 2H, H_(Ar)(HC═CBr)).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.6 (CH₃CH₂); 24.8 (CH₃CO); 31.3(CF₃CH(OAc)CH₂); 31.6 (CH₃SO₂); 34.0 (CHS); 48.6 (q, J=30 Hz, CF₃CH);52.3 (CH₂N); 70.0 (CH₂CH₃); 122.0 (Cq_(Ar.)Br); 129.9 (q, J=281 Hz,CF₃); 131.4 (CH_(Ar.) (HC═CNSO₂)); 133.53 (CH_(Ar.)(HC═CNSO₂)); 133.5(2×CH_(Ar.)(HC═CBr)); 146.5 (Cq_(Ar.)NSO₂); 180.0 (C═O); 213.1 (C═S).

IR (ν, cm⁻¹)(CCl₄) 2983; 1705 (C═O); 1439; 1358; 1226; 1184; 1162; 1135;1110; 1039; 1008.

Mass (IC, NH3) 553 (MH⁺); 570 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 36.96 3.83 Actual(%) 36.75 3.89Second Diastereoisomer

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.25 (t, J=7.0 Hz, 3H, CH₂CH₃); 1.96 (s,3H, COCH₃); 2.24-2.31 (m, 2H, CF3CH(OAc)CH₂); 2.87 (s, 3H, SO₂CH₃);3.51-3.59 (m, 1H, CHS); 3.78-3.83 (m, 2H, CH₂N); 4.27 (q, J=7.0 Hz 2H,CH₃CH₂); 4.61-4.65 (m, 1H, CF₃CH); 7.18 (d, J=8.0 Hz, 2H,H_(Ar)(HC═CNSO₂)); 7.51 (d, J=8.0 Hz, 2H, H_(Ar)(HC═CBr)).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.5 (CH₃CH₂); 22.5 (CH₃CO); 30.0(CF₃CH(OAc)CH₂); 31.5 (CH₃SO₂); 33.9 (CHS); 48.6 (q, J=30 Hz, CF₃CH);51.6 (CH₂N); 76.7 (CH₂CH₃); 122.0 (Cq_(Ar.)Br); 129.5 (q, J=281 Hz,CF₃); 131.2 (CH_(Ar.) (HC═CNSO₂)); 133.5 (CH_(Ar.) (HC═CNSO₂)); 133.5(2×CH_(Ar.)(HC═CBr)); 146.1 (Cq_(Ar.) NSO₂); 179.9 (C═O); 213.0 (C═S).

IR (ν, cm⁻¹)(CCl₄) 2987; 1709 (C═O); 1442; 1354; 1221; 1178; 1157; 1117;1035; 1001.

Mass (IC, NH3) 553 (MH⁺); 570 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 36.96 3.83 Actual(%) 36.87 3.74

Conversions of the Adducts Example 384-acetoxy-5,5,5-trifluoro-pent-1-ene

C₇H₉F₃O₂ M=182.14 g.mol⁻¹Reaction: A normal solution of tetrabutylammonium fluoride in THF (265ml, 1.06 mmol) is added to a solution of xanthate of example 32 (200 mg,0.53 mmol) in tetrahydrofuran (3 ml). After 2 hours at ambienttemperature, the admixture is concentrated at reduced pressure beforebeing purified.Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 1/9).

Product:

Pale yellow oil.

Yield:

74%.

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 2.14 (s, 3H, OCOCH₃); 3.08-3.14 (m, 2H,CH₂); 3.65-3.72 (m, 1H, CH═CH₂); 4.43-4.47 (m, 2H, CH═CH₂); 4.58-4.63(m, 1H, CF₃CH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 19.7 (CH₂); 22.3 (CH₃CO); 67.5 (q, J=30Hz, CF₃CH); 69.8 (CH═CH₂); 102.5 (CH═CH₂); 123.8 (q, J=281 Hz, CF₃);170.2 (C═O).

IR (ν, cm⁻¹)(CCl₄) 2830; 2340; 1765 (C═O); 1431; 1385; 1272; 1195; 1128;985; 927.

Mass (IC, NH3) 183 (MH⁺); 200 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 46.06 4.77 Actual(%) 47.16 4.98

Example 391-[5-bromo-1-methanesulphonyl-2,3-dihydro-1H-indol-3-ylmethyl)-2,2,2-trifluoro-ethyl]ester of acetic acid

C₁₄H₁₅BrF₃NO₄S M=430.24 g.mol⁻¹Reaction:

LP is added, at a rate of 10 mol % (21 mg, 0.054 mmol) every hour, to asolution of the xanthate adduct of example 37 (300 mg, 0.54 mmol) in1,2-dichloroethane (4 ml), which solution has been degassed beforehandat reflux under argon. The reaction is stopped after 13 hours 30 minutesunder reflux and the addition of 120% of LP (258 mg, 0.65 mmol). Thereaction medium is then brought to ambient temperature and concentratedat reduced pressure before being purified.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 1/9).

Product:

Pale yellow oil.

Yield:

88% (admixture of 2 diastereoisomers at a ratio of 1/1)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.78-1.87 (m, 0.5H, CF₃CH(OAc)CH₂);1.86-1.93 (m, 0.5H, CF₃CH(OAc)CH₂); 1.98 (s, 1.5H, COCH₃); 2.01 (s,1.5H, COCH₃); 2.19-2.23 (m, 0.5H, CF₃CH(OAc)CH₂); 2.22-2.26 (m, 0.5H,CF₃CH(OAc)CH₂); 3.04 (s, 1.5H, SO₂CH₃); 3.06 (s, 1.5H, SO₂CH₃);3.65-3.70 (m, 0.5H, CHCH₂N); 3.71-3.74 (m, 0.5H, CHCH₂N); 3.87 (dd,J₁=10.1 Hz, J₂=9.9 Hz, 0.5H, CH₂N); 3.90 (dd, J₁=10.1 Hz, J₂=10.0 Hz,0.5H, CH₂N); 4.08 (dd, J₁=10.0 Hz, J₂=9.9 Hz, 0.5H, CH₂N); 4.10 (dd,J₁=10.0 Hz, J₂=10.0 Hz, 0.5H, CH₂N); 4.79-4.85 (m, 0.5H, CF₃CH);4.87-4.90 (m, 0.5H, CF₃CH); 7.25 (d, J=8.5 Hz, 0.5H, H_(Ar)(HC═CNSO₂));7.27 (d, J=8.6 Hz, 0.5H, H_(Ar)(HC═CNSO₂)); 7.40 (d, J=8.5 Hz, 0.5H,H_(Ar)(HC═CBr)); 7.42 (d, J=8.6 Hz, 0.5H, H_(Ar)(HC═CBr)); 7.70 (s,0.5H, H_(Ar)(HC═CBr)); 7.72 (s, 0.5H, H_(Ar)(HC═CBr)).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 22.8 (CH₃CO); 32.8 (0.5×CF₃CH(OAc)CH₂);33.1 (0.5×CF₃CH(OAc)CH₂); 34.4 (0.5×CH₂N); 34.6 (0.5×CH₂N); 36.8(0.5×CH₃SO₂); 36.9 (0.5×CH₃SO₂); 48.5 (q, J=30 Hz, 0.5×CF₃CH); 48.7 (q,J=30 Hz, 0.5×CF₃CH); 55.8 (0.5×CHCH₂N); 56.3 (0.5×CHCH₂N); 115.5(0.5×CH_(Ar.)═CNSO₂); 115.7 (0.5×CH_(Ar.)═CNSO₂); 116.3(0.5×Cq_(Ar.)Br); 116.6 (0.5×Cq_(Ar.)Br); 126.8 (q, J=281 Hz, 0.5×CF₃);127.0 (q, J=281 Hz, 0.5×CF₃); 128.3 (0.5×CH_(Ar.)═CBr); 128.5(0.5×CH_(Ar.)═CBr); 132.0 (0.5×CH_(Ar.)═CBr); 132.1 (0.5×CH_(Ar.)═CBr);137.5 (0.5×Cq_(Ar.)NSO₂); 137.8 (0.5×Cq_(Ar.)NSO₂); 142.8(0.5×Cq_(Ar.)); 143.0 (0.5×Cq_(Ar.)); 170.9 (0.5×C═O); 171.3 (0.5×C═O).

IR (ν, cm⁻¹) (CCl₄) 1759 (C═O); 1549; 1352; 1307; 1269; 1214; 1161;1128; 1112.

Mass (IC, NH3) 431 (MH⁺); 448 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 39.08 3.51 Actual(%) 39.17 3.63

Examples of Methods for Preparing Compounds Having the Formula (VIIIB)Example 40 2-benzoxy-3,3,3-trifluoro-1-trifluoromethyl-propyl ester ofbenzoic acid

C₁₈H₁₂F₆O₄ M=406.28 g.mol⁻¹Reaction:

LP is added, at a rate of 10 mol % (52 mg, 0.13 mmol) every 10 minutes,to a solution of xanthate of example 30 (430 mg, 1.3 mmol) inchlorobenzene (14 ml), which solution has been degassed beforehand atreflux under argon. The reaction is stopped after 4 hours under refluxand the addition of 140% of LP (724 mg, 1.8 mmol). The reaction mediumis then brought to ambient temperature and concentrated at reducedpressure before being purified.

Purification:

By means of precipitation in an admixture of ether-petroleum ether 5/95.

Product:

Colourless solid.

Yield:

65% (admixture of 2 diastereoisomers at a ratio of 1/1)

¹HNMR (δ, ppm) (CD₃)₂SO, 400 MHz) 4.57-4.64 (m, 1H, CF₃CH); 4.66-4.69(m, 1H, CF₃CH); 7.31-7.39 (m, 4H_(Ar), CH_(Ar)═CH_(Ar)═CH_(Ar)C_(qAr));7.48-7.53 (m, 2H_(Ar), CH_(Ar)═CH_(Ar)═CH_(Ar)C_(qAr)); 7.77-7.89 (m,4H_(Ar), CH_(Ar)═CH_(Ar)═CH_(Ar)C_(qAr)).

¹³CNMR (δ, ppm) ((CD₃)₂SO,400 MHz) 78.4 (q, J=31 Hz, CF₃CH); 79.8 (q,J=31 Hz, CF₃CH); 117.03 (q, J=283 Hz, CF₃); 118.09 (q, J=283 Hz, CF₃);126.4 (2×CH_(Ar)); 126.8 (2×CH_(Ar)); 129.1 (2×CH_(Ar)); 129.3(2×CH_(Ar)); 129.7 (2×CH_(Ar)); 131.5 (C_(qAr)); 131.8 (C_(qAr)); 159.5(C═O); 160.0 (C═O).

IR (ν, cm⁻¹) (nujol) 2976; 1702 (C═O); 1547; 1340; 1301; 1255; 1238;1181; 1153; 1108.

Mass (IC, NH3) 407 (MH⁺); 424 (MNH₄ ⁺).

Examples of the Method for Preparing Compounds Having the Formula (IC)Synthesis of 2-trifluoromethylethylchloro xanthate Example 41 O-ethyland S-1-chloro-2,2,2-trifluoro-ethyl diester of dithiocarbonic acid

a) O-ethyl and S-1-hydroxy-2,2,2-trifluoro-ethyl diester ofdithiocarbonic acid

C₅H₇F₃O₂S₂ M=220.23 g.mol⁻¹Reaction:

The salt of potassium ethylxanthogenate (737 mg, 4.62 mmol) is added toa solution of 2,2,2-trifluoro-1-methoxy-ethanol (300 mg, 2.31 mmol) inacetone (5 ml). The reaction admixture is cooled to 0° C. and sulphuricacid (123.6 μL, 2.31 mmol) is added drop by drop. After one hour at 0°C., the reaction admixture is concentrated at reduced pressure. Theresidue is placed in ether, filtered and concentrated again at reducedpressure.

Product:

Yellow oil.

Yield:

69%

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.54 (t, J=6.3 Hz, 3H, CH₂CH₃); 4.71 (q,J=6.3 Hz, 2H, CH₃CH₂); 6.02 (q, J=5.71 Hz, 1H, CF₃CH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.7 (CH₃CH₂); 57.8 (q, J=30 Hz,CF₃CH); 71.4 (CH₂CH₃); 124.4 (q, J=280 Hz, CF₃); 207.1 (C═S).

IR (ν, cm⁻¹)(CCl₄) 2961; 1453; 1314; 1231; 1130; 1052; 1023.

Mass (IC, NH3) 221 (MH⁺), 238 (MNH₄ ⁺).

b) O-ethyl and S-1-chloro-2,2,2-trifluoro-ethyl diester ofdithiocarbonic acid

C₅H₆ClF₃OS₂ M=238.68 g.mol⁻¹Reaction:

A solution of alcohol 41a) (1.38 g, 6.3 mmol) and phosphoruspentachloride (1.30 g, 6.3 mmol) is agitated at ambient temperature for1 hour. After evaporation at reduced pressure, the residue is purified.

Purification:

Chromatography over silica gel (petroleum ether and ethyl acetate 1/9then 2/8).

Product:

Yellow oil.

Yield:

18%

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.49 (t, J=6.8 Hz, 3H, CH₂CH₃); 4.75 (q,J=6.8 Hz, 2H, CH₃CH₂); 6.27 (q, J=8.4 Hz,1H, CF₃CH).

¹³CNMR (δ, ppm)(CDCl₃, 100 MHz) 13.9 (CH₃CH₂); 22.6 (q, J=35 Hz, CF₃CH);71.5 (CH₂CH₃); 121.1 (q, J=282 Hz, CF₃); 211.1 (C═S).

IR (ν, cm⁻¹)(CCl₄) 2986; 2939; 1442; 1370; 1344; 1194; 1131; 1032; 868;823.

Mass (IC, NH3) 238 (M), 240 (M+2); 193 (MH+-EtOH).

Microanalysis Element: Carbon Hydrogen Calculated (%) 25.16 2.53 Actual(%) 25.19 2.51

Radical Additions Examples of Methods for Preparing Compounds Having theFormula (IIc)

The general operating method is as set out above for the preparation ofthe compounds (IIa).

Example 42 O-ethyl andS-3-chloro-4,4,4-trifluoro-1-trimethylsilanylmethylbutyl diester ofdithiocarbonic acid

C₁₁H₂₀ClF₃OS₂Si M=352.94 g.mol⁻¹Reaction:

Carried out according to the general operating method with 133 mg (0.64mmol) of xanthate of example 41 and 220 mg (2.29 mmol) ofallyltrimethylsilane in 1,2-dichloroethane (2 ml). The reaction isterminated after the addition of 5% of LP (13 mg) and 1 hour 30 minutesunder reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 1/9).

Product:

Yellow oil.

Yield:

88% (admixture of 2 diastereoisomers at a ratio of 2/3)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 0.12 (s, 3.6H, Si(CH₃)₃); 0.31 (s, 5.4H,Si(CH₃)₃); 1.13-1.18 (m, 0.8H, CH₂Si(CH₃)₃); 1.30-1.35 (m, 1.2H,CH₂Si(CH₃)₃); 1.48 (t, J=7.0 Hz, 3H, CH₂CH₃); 2.08-2.14 (m, 0.8H,CF₃CHClCH₂); 2.24-2.29 (m, 1.2H, CF₃CHClCH₂); 4.01-4.08 (m,0.4H, CHS);4.10-4.15 (m, 0.6H, CHS); 4.18-4.23 (m, 0.4H, CF₃CH); 4.27-4.35 (m,0.6H, CF₃CH); 4.69-4.76 (m, 2H, CH₃CH₂);

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) −0.7 (1.2×Si(CH₃)₃); −0.8(1.8×Si(CH₃)₃); 13.9 (CH₃CH₂); 27.3 (0.4×CH₂Si(CH₃)₃); 28.2(0.6×CH₂Si(CH₃)₃); 33.3 (0.4×CH₂CF₃CHCl); 35.5 (0.6×CH₂CF₃CHCl); 43.3(0.4×CHS); 47.4 (0.6×CHS); 51.3 (q, J=28 Hz, 0.4×CF₃CH); 52.4 (q, J=28Hz, 0.6×CF₃CH); 70.5 (CH₂CH₃); 120.3 (q, J=281 Hz, 0.4×CF₃); 122.4 (q,J=281 Hz, 0.6×CF₃); 213.1 (0.4×C═S); 215.2 (0.6×C═S).

IR (ν, cm⁻¹) (CCl₄) 2956; 1471; 1441; 1415; 1373; 1328; 1313; 1220;1178; 1123; 1051; 982; 937.

Mass (IC, NH3) 354 (MH⁺); 371 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 37.43 5.71 Actual(%) 37.66 5.94

Example 43 4-chloro-2-ethoxythiocarbonylsulphanyl-5,5,5-trifluoro-pentylester of acetic acid

C₁₀H₁₄ClF₃O₃S₂ M=338.80 g.mol⁻¹Reaction:

Carried out according to the general operating method with 200 mg (0.84mmol) of xanthate of example 41 and 232 μL (2.5 mmol) of allyl acetatein 1,2-dichloroethane (2 ml). The reaction is terminated after theaddition of 5% of LP (17 mg) and 1 hour 30 minutes under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 1/9).

Product:

Pale yellow oil.

Yield:

74% (2 diastereoisomers at a ratio of 6/1).

First Diastereoisomer (Majority)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.44 (t, J=7.0 Hz, 3H, CH₂CH₃); 2.06 (s,3H, COCH₃); 2.35-2.55 (m, 2H, CF₃CHClCH₂); 4.18-4.22 (m, 1H, CHS);4.30-4.35 (m, 2H, CH₂OCOCH₃); 4.43 (q, J=7.0 Hz, 2H, CH₃CH₂); 4.49-4.55(m, 1H, CF₃CH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.1 (CH₃CH₂); 20.7 (CH₃CO); 32.0(CF₃CHClCH₂); 42.3 (CHS); 56.3 (q, J=28 Hz, CF₃CH); 64.0 (CH₂OCOCH₃);70.5 (CH₂CH₃); 118.7 (q, J=281 Hz, CF₃); 169.1 (C═O); 210.3 (C═S).

IR (ν, cm⁻¹) (CCl₄) 2984; 1751 (C═O); 1461; 1438; 1379; 1363; 1310;1266; 1228; 1185; 1130; 1050.

Mass (IC, NH3) 339 (MH⁺); 356 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 35.44 4.17 Actual(%) 35.17 4.08Second Diastereoisomer (Minority)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.46 (t, J=7.0 Hz, 3H, CH₂CH₃); 2.11 (s,3H, COCH₃); 2.21-2.31 (m, 2H, CF₃CHClCH₂); 4.17-4.22 (m, 1H, CHS);4.29-4.37 (m, 2H, CH₂OCOCH₃); 4.45 (q, J=7.0 Hz, 2H, CH₃CH₂); 4.51-4.58(m, 1H, CF₃CH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.2 (CH₃CH₂); 20.9 (CH₃CO); 31.1(CF₃CHClCH₂); 43.5 (CHS); 58.4 (q, J=28 Hz, CF₃CH); 66.1 (CH₂OCOCH₃);68.1 (CH₂CH₃); 120.4 (q, J=281 Hz, CF₃); 170.2 (C═O); 212.4 (C═S).

IR (ν, cm⁻¹)(CCl₄) 2980; 1749 (C═O); 1450; 1437; 1357; 1308; 1264; 1225;1183; 1135; 1047.

Mass (IC, NH3) 339 (MH⁺); 356 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 35.44 4.17 Actual(%) 35.46 4.12

Example 44 O-ethyl andS-3-chloro-1-(1,3-dioxo-1,3-dihydro-isoindol-2-ylmethyl)4,4,4-trifluoro-butylester of dithiocarbonic acid

C₁₆H₁₅ClF₃NO₃S₂ M=425.88 g.mol⁻¹Reaction:

Carried out according to the general operating method with 200 mg (0.84mmol) of xanthate of example 41 and 427 mg (2.5 mmol) ofN-allylphthalimide in 1,2-dichloroethane (2 ml). The reaction isterminated after the addition of 10% of LP and 3 hours under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 5/95).

Product:

Translucent crystals.

Yield:

65% (admixture of 2 diastereoisomers at a ratio of 1/1).

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.37-1.43 (m, 3H, CH₂CH₃); 2.15-2.24 (m,0.5H, CF₃CHClCH₂); 2.29-2.33 (m, 1H, CF₃CHClCH₂); 2.39-2.43 (m, 0.5H,CF3CHClCH₂); 3.93-4.02 (m, 2H, CH₂N); 4.01-4.06 (m, 1H, CH₃CH₂);4.04-4.14 (m, 1H, CH₃CH₂); 4.31-4.38 (m, 0.5H, CHS); 4.38-4.47 (m, 0.5H,CHS); 5.49-5.56 (m, 0.5H, CF₃CH); 5.59-5.66 (m, 0.5H, CF₃CH); 7.72-7.74(m, 2H, H_(Ar.)(C_(q)CH═CH)); 7.76-7.84 (m, 2H, H_(Ar.)(C_(q)CH═CH)).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 12.2 (0.5×CH₃CH₂); 12.3 (0.5×CH₃CH₂);30.8 (0.5×CF₃CHClCH₂); 31.5 (0.5×CF₃CHClCH₂); 38.7 (0.5×CH₂N); 39.5(0.5×CH₂N); 43.5 (0.5×CHS); 44.0 (0.5×CHS); 49.5 (q, J=31 Hz,0.5×CF₃CH); 50.0 (q, J=35 Hz, 0.5×CF₃CH); 115.9 (0.5×CH₂CH₃); 116.0(0.5×CH₂CH₃); 118.4 (q, J=278 Hz, 0.5×CF₃); 120.3 (q, J=278 Hz,0.5×CF₃); 129.8 (2×Cq_(Ar.)); 132.8 (2×CH_(Ar.)(C_(q)CH═CH)); 133.2(2×CH_(Ar.)(C_(q)CH═CH)); 159.3 (C═O_(Ar.)); 162.4 (C═O_(Ar.)); 211.5(0.5×C═S); 212.7 (0.5×C═S).

IR (ν, cm⁻¹)(CCl₄) 2926; 1776; 1722 (C═O); 1430; 1391; 1328; 1265; 1223;1189; 1131; 1112; 1048; 887.

Mass (IC, NH3) 427 (MH⁺); 444 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 49.64 3.82 Actual(%) 49.51 3.93

Example 45 O-ethyl andS-1-(2-chloro-3,3,3-trifluoro-propyl)-4-oxo-pentyl diester ofdithiocarbonic acid

C₁₁H₁₆Cl₃O₂S₂ M=336.83 g.mol⁻¹Reaction:

Carried out according to the general operating method with 450 mg (1.89mmol) of xanthate of example 41 and 657 μL (5.67 mmol) of hex-5-en-2-onein 1,2-dichloroethane (4 ml). The reaction is terminated after theaddition of 10% of LP (75 mg) and 3 hours 15 minutes under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 5/95).

Product:

Dark yellow oil.

Yield:

55% over the four steps, relative to the hemiacetaltrifluoroacetaldehyde (admixture of 2 diastereoisomers at a ratio of1/1)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 0.95 (t, J=7.0 Hz, 1.5H, CH₂CH₃); 0.98(t, J=7.0 Hz, 1.5H, CH₂CH₃); 1.19-1.25 (m, 1H, CH₂COCH₃); 1.35 (s, 1.5H,COCH₃); 1.36 (s, 1.5H, COCH₃); 1.35-1.39 (m, 1H, CH₂COCH₃); 1.41-1.47(m, 2H, CH₂CH₂COCH₃); 1.69-1.74 (m, 2H, CH₂CHCF₃); 3.10 (q, J=7.0 Hz,1H, CH₃CH₂); 3.12 (q, J=7.0 Hz, 1H, CH₃CH₂); 3.39-3.46 (m, 0.5H, CHS);3.51-3.53 (m, 0.5H, CHS); 4.54-4.59 (m, 0.5H, CF₃CH); 4.59-4.61 (m,0.5H, CF₃CH).

¹³CNMR (δ, ppm)(CDCl₃, 100 MHz) 13.8 (CH₃CH₂); 22.5 (0.5×CH₂COCH₃); 22.7(0.5×CH₂COCH₃); 28.2 (0.5×CH₃CO); 28.3 (0.5×CH₃CO); 29.0(0.5×CHCH₂COCH₃); 29.2 (0.5×CH₂CH₂COCH₃); 29.3 (0.5×CH₂CHCF₃); 29.4(0.5×CH₂CHCF₃); 31.8 (0.5×CHS); 32.1 (0.5×CHS); 35.7 (q, J=31 Hz,0.5×CF₃CH); 35.8 (q, J=31 Hz, 0.5×CF₃CH); 69.6 (0.5×CH₂CH₃); 70.2(0.5×CH₂CH₃); 126.8 (q, J=281 Hz, 0.5×CF₃); 127.3 (q, J=281 Hz,0.5×CF₃); 208.2 (0.5×C═O); 209.3 (0.5×C═O); 215.1 (0.5×C═S); 216.2(0.5×C═S).

IR (ν, cm⁻¹)(CCl₄) 2926; 2854; 1691 (C═O); 1465; 1216; 1112; 1052.

Mass (IC, NH3) 337 (MH⁺), 354 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 39.23 4.79 Actual(%) 39.03 4.73

Example 46 Dimethyl and4-chloro-2-ethoxythiocarbonylsulphanyl-5,5,5-trifluoro-pentyl ester ofphosphonic acid

C₁₀H₁₇ClF₃O₄PS₂ M=388.79 g.mol⁻¹Reaction:

Carried out according to the general operating method with 450 mg (1.89mmol) of xanthate of example 41 and 529 μL (5.67 mmol) of dimethylallylphosphate in 1,2-dichloroethane (2 ml). The reaction is terminated afterthe addition of 10% of LP (75 mg) and 3 hours 15 minutes under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 1/9) thenincrease of polarity up to pure ethyl acetate.

Product:

Dark yellow oil.

Yield:

27% over the four steps (2 diastereoisomers at a ratio of 3/2).

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.21-1.27 (m, 1.8H, CH₂CH₃); 1.25-1.30(m, 1.2H, CH₂CH₃); 2.20-2.27 (m, 1H, CHS); 3.31-3.39 (m, 1.2H,CF₃CHClCH₂); 3.49-3.54 (m, 0.8H, CF₃CHClCH₂); 3.54-3.59 (m, 2H, CH₂P);3.65-3.69 (m, 3H, OCH₃); 3.69-3.74 (m, 3H, OCH₃); 4.51-4.57 (m, 1.2H,CH₃CH₂); 4.59-4.65 (m, 0.8H, CH₃CH₂); 5.81-5.88 (m, 1H, CF₃CH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 12.8 (0.4×CH₃CH₂); 13.0 (0.6×CH₃CH₂);21.3 (0.4×OCH₃); 22.7 (0.6×OCH₃); 23.5 (0.4×OCH₃); 24.3 (0.6×OCH₃); 27.4(d, J=134 Hz, 0.4×CH₂P); 28.1 (d, J=138 Hz, 0.6×CH₂P); 29.3 (q, J=30 Hz,0.4×CF₃CH); 30.1 (q, J=30 Hz, 0.6×CF₃CH); 31.3 (0.4×CF₃CHClCH₂); 31.4(0.6×CF₃CHClCH₂); 32.0 (0.4×CHS); 32.3 (0.6×CHS); 67.0 (0.4×CH₂CH3);70.3 (0.6×CH₂CH₃); 123.4 (q, J=278 Hz, 0.4×CF₃); 124.5 (q, J=278 Hz,0.6×CF₃); 212.0 (0.4×C═S); 212.1 (0.6×C═S).

IR (ν, cm⁻¹) (CCl₄) 2957; 2928; 2855; 1732; 1710; 1263; 1235; 1135;1043.

Mass (IC, NH3) 390 (MH⁺); 268 (MH⁺-HSCSOEt).

Example 47 O-ethyl and S-3-chloro-1-cyanomethyl-4,4,4-trifluoro-butyldisester of dithiocarbonic acid

C₉H₁₁ClF₃NOS₂ M=305.77 g.mol⁻¹Reaction:

Carried out according to the general operating method with 450 mg (1.89mmol) of xanthate of example 41 and 109 μL (5.67 mmol) ofbut-3-enenitrile in 1,2-dichloroethane (4 ml). The reaction isterminated after the addition of 10% of LP (75 mg) and 3 hours 15minutes under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 2/8).

Product:

Dark yellow oil.

Yield:

52% over the 4 steps (admixture of 2 diastereoisomers at a ratio of 2/1)

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.41 (t, J=5.7 Hz, 2H, CH₂CH₃); 1.45 (t,J=5.7 Hz, 1H, CH₂CH₃); 2.12-2.63 (m, 2H, CF₃CHClCH₂); 3.00-3.06 (m, 2H,CH₂CN); 3.99-4.04 (m, 0.3H, CHS); 4.07-4.12 (m, 0.7H, CHS); 4.38-4.42(m, 0.3H, CF₃CH); 4.46-4.53 (m, 0.7H, CF₃CH); 4.71 (q, J=5.7 Hz, 0.7H,CH₃CH₂); 4.74 (q, J=5.7 Hz, 1.3H, CH₃CH₂).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.7 (CH₃CH₂); 23.1 (0.3×CH₂CF₃CHCl);25.2 (0.7×CH₂CF₃CHCl); 25.4 (0.3×CH₂CN); 30.5 (0.7×CH₂CN); 41.0(0.3×CHS); 42.0 (0.7×CHS); 52.4 (q, J=43 Hz, 0.3×CF₃CH); 53.7 (q, J=43Hz, 0.7×CF₃CH); 70.9 (0.3×CH₂CH₃); 71.0 (0.7×CH₂CH₃); 115.5 (0.3×CN);116.1 (0.7×CN); 122.3 (q, J=286 Hz, 0.3×CF₃); 124.4 (q, J=286 Hz,0.7×CF₃); 209.4 (0.3×C═S); 210.3 (0.7×C═S).

IR (ν, cm⁻¹) (CCl₄) 2926; 1745; 1266; 1237; 1180; 1130; 1050.

Mass (IC, NH3) 306 (MH⁺); 323 (MNH₄ ⁺).

Example 48 O-ethyl andS-3-chloro-1-diethoxymethyl-4,4,4-trifluoro-pentyl diester ofthiocarbonic acid

C₁₃H₂₂ClF₃O₃S₂ M=382.89 g.mol⁻¹Reaction:

Carried out according to the general operating method with 400 mg (1.69mmol) of xanthate of example 41 and 730 mg (5.67 mmol) of4,4-diethoxy-butene in 1,2-dichloroethane (4 ml). The reaction isterminated after the addition of 15% of LP (101 mg) and 4 hours 45minutes under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 5/95).

Product:

Thick pale yellow oil.

Yield:

49% over the 4 steps (2 diastereoisomers at a ratio of 1/1)

First Diastereoisomer

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.26 (t, J=8.2 Hz, 3H, CH₂CH₃);1.37-1.42 (m, 2H, CH—CH₂—CH(OEt)₂); 1.53 (t, J=8.1 Hz, 6H, 2×CH₂CH₃);1.66-1.71 (m, 2H, CF₃CHClCH₂); 3.17 (t,1H, J=8.2 Hz, CH(OEt)₂);3.47-3.53 (m, 1H, CHS); 4.62 (q, J=8.2 Hz, 2H, CH₃CH₂O); 4.74 (q, J=8.1Hz, 4H, 2×CH₃CH₂O); 6.31 (q, J=7.8 Hz, 1H, CF₃CH).

¹³CNMR (δ, ppm)(CDCl₃, 100 MHz) 13.8 (2×CH₃CH₂); 14.2 (CH₃CH₂); 22.6(CH—CH₂—CH—(OEt)₂); 28.3 (CH₂CHS); 29.6 (q, J=30 Hz, CF₃CH); 31.8 (CHS);35.8 (CH₂CH₃); 35.9 (CH₂CH₃); 69.7 (CH₂CH₃); 100.8 (CH(OEt)₂); 124.5 (q,J=281 Hz, CF₃); 215.2 (C═S).

IR (ν, cm⁻¹) (CCl₄) 2957; 2927; 2855; 1705; 1465; 1442; 1367; 1293;1243; 1217; 1189; 1113; 1050.

Mass (IC, NH3) 384 (M−H⁺); 338 (MH+-EtOH).

Microanalysis Element: Carbon Hydrogen Calculated (%) 40.78 5.79 Actual(%) 40.63 5.42Second Diastereoisomer

¹HNMR (δ, ppm)(CDCl₃, 400 MHz) 1.26 (t, J=8.2 Hz, 3H, CH₂CH₃); 1.41-1.47(m, 2H, CH—CH₂—CH(OEt)₂); 1.56 (t, J=8.0 Hz, 6H, 2×CH₂CH₃); 1.61-1.68(m, 2H, CF₃CHClCH₂); 3.67-3.72 (m, 1H, CH(OEt)₂); 3.85-3.92 (m, 1H,CHS); 4.71 (q, J=8.2 Hz, 2H, CH₃CH₂O); 4.78 (q, J=8.0 Hz, 4H,2×CH₃CH₂O); 6.12 (q, J=7.8 Hz, 1H, CF₃CH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.7 (2×CH₃CH₂); 14.0 (CH₃CH₂); 22.5(CH—CH₂—CH—(OEt)₂); 28.4 (CH₂CHS); 29.3 (q, J=30 Hz, CF₃CH); 31.6 (CHS);34.7 (CH₂CH₃); 34.8 (CH₂CH₃); 69.5 (CH₂CH₃); 100.3 (CH(OEt)₂); 123.9 (q,J=281 Hz, CF₃); 216.0 (C═S).

IR (ν, cm⁻¹)(CCl₄) 2963; 2931; 2851; 1701; 1467; 1448; 1295; 1257; 1219;1195; 1115; 1057.

Mass (IC, NH3) 384 (M—H⁺); 338 (MH+-EtOH).

Microanalysis Element: Carbon Hydrogen Calculated (%) 40.78 5.79 Actual(%) 40.67 5.34

Example 49 O-ethyl andS-3-chloro-1-(4-chlorophenoxymethyl)-4,4,4-trifluoro-butyl diester ofdithiocarbonic acid

C₁₄H₁₅C₂F₃O₂S₂ M=407.35 g.mol⁻¹Reaction:

Carried out according to the general operating method with 400 mg (1.69mmol) of xanthate of example 41 and 852 mg (5.67 mmol) of1-allyloxy-4-chloro-benzene in 1,2-dichloroethane (4 ml). The reactionis terminated after the addition of 15% of LP (338 mg) and 4 hours 45minutes under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 2/98).

Product:

Pale yellow oil.

Yield:

28% over the four steps (admixture of 2 diastereoisomers at a ratio of2/1).

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 1.37 (t, J=8.3 Hz, 3H, CH₂CH₃);1.47-1.51 (m, 0.7H, CF₃CHClCH₂); 1.51-1.58 (m, 1.3H, CF₃CHClCH₂);3.01-3.09 (m, 2H, OCH₂CHS); 3.57 (q, J=8.3 Hz, 2H, CH₃CH₂); 4.01-4.13(m, 0.3H, CHS); 4.13-4.21 (m, 0.7H, CHS); 4.73 (q, J=5.5 Hz, 0.3H,CF₃CH); 4.94 (q, J=5.5 Hz, 0.7H, CF₃CH); 6.75-6.85 (m, 2H,H_(Ar.)(CH═CCl)); 7.13-7.27 (m, 2H, H_(Ar.)(CH═CO)).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 13.5 (0.3×CH₃CH₂); 13.6 (0.7×CH₃CH₂);23.0 (0.3×CH₂CHCF₃); 23.0 (0.7×CH₂CHCF₃); 28.7 (0.3×CHS); 28.9(0.7×CHS); 29.2 (q, J=32 Hz, 0.3×CF₃CH); 29.2 (q, J=32 Hz, 0.7×CF₃CH);32.1 (0.3×CH₂O); 32.2 (0.7×CH₂O); 63.4 (0.3×CH₂CH₃); 63.5 (0.7×CH₂CH₃);116.2 (C_(qAr)Cl); 128.2 (q, J=284 Hz, 0.3×CF₃); 128.4 (q, J=284 Hz,0.7×CF₃); 130.3 (C_(Ar)H, CH═CCl); 130.4 (C_(Ar.)(CH═CCl)); 132.7(2×C_(Ar.)(CH═CO)); 137.3 (0.3×C_(qAr)O); 137.4 (0.7×C_(qAr)O); 210.7(0.3×C═S); 211.3 (0.7×C═S).

IR (ν, cm⁻¹)(CCl₄) 2926; 2358; 2350; 1552; 1492; 988; 962.

Mass (IC, NH3) 408 (MH⁺); 425 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 41.29 3.71 Actual(%) 41.01 3.57

Example 50 O-ethyl andS-3-chloro-4,4,4-trifluoro-1-(2-oxo-pyrrolidin-1-yl)-butyl ester ofdithiocarbonic acid di

C₁₁H₁₅ClF₃NO₂S₂ M=350.83 g.mol⁻¹Reaction:

Carried out according to the general operating method with 400 mg (1.69mmol) of xanthate of example 41 and 563 mg (5.07 mmol) ofvinyl-pyrrolidin-2-one in 1,2-dichloroethane (4 ml). The reaction isterminated after the addition of 15% of LP (100 mg) and 4 hours 45minutes under reflux.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 1/9).

Product:

Pale yellow oil.

Yield:

22% over the four steps (admixture of 2 diastereoisomers at a ratio of1/1).

¹HNMR (δ, ppm) CDCl₃, 400 MHz) 1.94 (t, J=7.0 Hz, 1.5H, CH₂CH₃); 2.01(t, J=7.0 Hz, 1.5H, CH₂CH₃); 2.43 (m, 2H, CH₂CH₂CH₂); 2.51 (m, 2H,CH₂C═O); 3.24-3.37 (m, 2H, NCH₂); 3.41-3.55 (m, 2H, CF₃CHClCH₂); 3.77(q, J=7.0 Hz, 1H, CH₃CH₂); 3.83 (q, J=7.0 Hz, 1H, CH₃CH₂); 6.12-6.16 (m,0.5H, CHS); 6.17-6.21 (m, 0.5H, CHS); 7.08-7.15 (m, 0.5H, CF₃CH);7.19-7.24 (m, 0.5H, CF₃CH).

¹³CNMR (δ, ppm) CDCl₃, 100 MHz) 17.3 (0.5×CH₃CH₂); 18.4 (0.5×CH₃CH₂);28.0 (0.5×CH₂CH₂CH₂); 28.4 (0.5×CH₂CH₂CH₂); 29.1 (0.5×CH₂C═O); 29.2(0.5×CH₂C═O); 30.4 (0.5×CF₃CHClCH₂); 30.6 (0.5×CF₃CHClCH₂); 43.1(0.5×CH₂N); 43.5 (0.5×CH₂N); 44.3 (q, J=28 Hz, 0.5×CF₃CH); 46.3 (q, J=28Hz, 0.5×CF₃CH); 57.5 (0.5×CHS); 58.4 (0.5×CHS); 70.5 (0.5×CH₂CH₃); 70.6(0.5×CH₂CH₃); 127.4 (q, J=275 Hz, 0.5×CF₃); 128.4 (q, J=275 Hz,0.5×CF₃); 177.8 (0.5×C═O); 178.3 (0.5×C═O); 218.1 (0.5×C═S); 220.1(0.5×C═S).

IR (ν, cm⁻¹)(CCl₄) 2926; 2335; 1702 (C═O); 1260; 1114; 1049.

Mass (IC, NH3) 352 (MH⁺); 369 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 37.66 4.60 Actual(%) 37.63 4.49

Conversion of Adducts Example 511-(3-chloro-4,4,4-trifluoro-but-1-enyl)-pyrrolidin-2-one

C₈H₉ClF₃NO M=227.62 g.mol⁻¹Reaction:

A solution of xanthate of example 50 (200 mg, 0.57 mmol) inchlorobenzene (5 ml) is brought to reflux for 2 hours. The crudereaction product is brought to ambient temperature then concentrated atreduced pressure before being purified.

Purification:

Chromatography over silica gel (dichloromethane-methanol 98/2).

Product:

Pale yellow oil.

Yield:

Quantitative

¹HNMR (δ, ppm) (CDCl₃, 400 MHz) 2.07-2.12 (m, 2H, CH₂CH₂CH₂); 2.45-2.53(m, 2H, CH₂C═O); 2.87-2.93 (m, 2H, NCH₂); 4.69-4.77 (m, 1H, CF₃CH); 6.75(dd, J₁=13.3 Hz, J₂=6.1 Hz, 1H, CH═CHN); 7.41 (d, J=13.3 Hz, 1H,NCH═CH).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 22.3 (CH₂CH₂CH₂); 28.8 (CH₂CO); 33.4(CH₂N); 45.1 (q, J=28 Hz, CF₃CH); 115.1 (CH═CHN); 119.1 (NCH═CH); 141.5(q, J=275 Hz, CF₃); 174.3 (C═O).

IR (ν, cm⁻¹)(CCl₄) 2926; 2854; 2359; 1741 (C═O); 1699; 1594; 1460; 1407;1362; 1193.

Mass (IC, NH3) 228 (MH⁺); 244 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 42.22 3.99 Actual(%) 42.09 3.87

Example 52 2-(4-chloro-5,5,5-trifluoro-pentyl)-isoindole-1,3-dione

C₁₃H₁₁ClF₃NO₂ M=305.69 g.mol⁻¹Reaction:

LP is added, at a rate of 10 mol % (26 mg, 0.032 mmol) every hour, to asolution of the xanthate adduct of example 44 (134 mg, 0.32 mmol) inpropan-2-ol (2 ml), which solution has been degassed beforehand atreflux under argon.

The reaction is stopped after 13 hours under reflux and the addition of110% of LP (140 mg, 0.35 mmol). The reaction medium is then brought toambient temperature and concentrated at reduced pressure before beingpurified.

Purification:

Chromatography over silica gel (ethyl acetate-petroleum ether 2/98).

Product:

Translucent crystals.

Yield:

78%

¹H NMR (δ, ppm) (CDCl₃, 400 MHz) 1.57-1.63 (m, 2H, CF₃CHClCH₂);2.26-2.32 (m, 2H, CH₂CH₂N); 3.93-4.02 (t, J=6.5 Hz, 2H, CH₂N); 7.17-7.23(m, 1H, CF₃CH); 7.62-7.71 (m, 2H, H_(Ar.)(C_(q)CH═CH)); 7.73-7.84 (m,2H, H_(Ar)(C_(q)CH═CH)).

¹³CNMR (δ, ppm) (CDCl₃, 100 MHz) 25.1 (CH₂CH₂N); 28.5 (CF₃CHClCH₂); 39.8(CH₂N); 49.5 (q, J=31 Hz, CF₃CH); 123.5 (2×CH_(Ar.)(C_(q)CH═CH)); 125.0(q, J=281 Hz, CF₃); 133.5 (2×Cq_(Ar.)); 148.5 (2×CH_(Ar.)(C_(q)CH═CH));168.8 (2×C═O_(Ar.)).

IR (ν, cm⁻¹)(CCl₄) 2940; 1774; 1502; 1408; 1373; 1346; 1245; 1167; 1127.

Mass (IC, NH3) 307 (MH⁺); 323 (MNH₄ ⁺).

Microanalysis Element: Carbon Hydrogen Calculated (%) 51.08 3.63 Actual(%) 51.01 3.58

1. Compound having the formula (I):

in which X represents a —NZ₂Z₃, —OZ₅ group or a halogen atom (Hal)selected from Cl, Br and I, in which Z₂ and Z₃ represent, independentlyof each other, a hydrogen atom, a group selected from the alkyls,cycloalkyls, aryls and the electroattractive groups, wherein at leastone of the radicals Z₂ and Z₃ advantageously has an electroattractiveeffect with respect to the electron density of the nitrogen atom towhich they are bonded, Z₂ and Z₃ can be bonded in order to form aheterocycle with the nitrogen atom, Z₅ represents a hydrogen atom, agroup selected from the alkyls, cycloalkyls, aryls or the groups whichare electroattractive with respect to the electron density of the oxygenatom to which it is bonded, Z₁ represents a group selected from: (i) thealkyl, acyl, aryl, aralkyl, alkene or alkyne groups, the cyclichydrocarbons and the heterocycles, (ii) a —OR^(a) or —SR^(a) group inwhich R^(a) is a group selected from: an alkyl, halogenoalkyl, alkenyl,alkynyl, acyl, aryl, arylalkyl, arylalkenyl, arylalkynyl group, or acyclic hydrocarbon or a heterocycle, or a polymer chain; a—CR^(b)R^(c)PO(OR^(d))(OR^(e)) group in which: R^(b) and R^(c) eachrepresent, independently of each other, a hydrogen atom, a halogen atom,an alkyl group, perfluoroalkyl, a cyclic hydrocarbon or a heterocycle,or an —NO₂, —NCO, CN group, or a group selected from —R^(f), —SO₃R^(f),—OR^(f), —SR^(f), —NR^(f)R^(g), —COOR^(f), —O₂CR^(f), —CONR^(f)R^(g),—NCOR^(f)R^(g), in which R^(f) and R^(g) each independently refer to analkyl, alkenyl, alkynyl, cycloalkenyl, cycloalkynyl, aryl group which isoptionally condensed to a heterocycle, alkaryl, arylalkyl, heteroaryl,or R^(b) and R^(c) form, together with the carbon atom to which they areattached, a C═O or C═S group or a cyclic hydrocarbon or a heterocycle;and R^(d) and R^(e) each represent, independently of each other, aradical which complies with one of the definitions given above for thegroup R^(f); or R^(d) and R^(e) together form a hydrocarbon chain whichcomprises from 2 to 4 carbon atoms, and which is optionally interruptedby a group selected from —O—, —S— and —NR^(h)—; in which R^(h) complieswith one of the definitions given above for the group R^(f); (iii) agroup —NR^(i)R^(j), in which: R^(i) and R^(j) represent, independentlyof each other, a radical selected from an alkyl, halogenoalkyl, alkenyl,alkynyl, acyl, ester, aryl, arylalkyl, arylalkenyl, arylalkynyl group,or a cyclic hydrocarbon or a heterocycle; or R^(i) and R^(j) togetherform a hydrocarbon chain which comprises from 2 to 4 carbon atoms andwhich is optionally interrupted by a —O—, —S—, or —NR^(H)—, or R^(H)group which complies with one of the definitions given above for theR^(f) group, Z₄ represents a hydrogen atom, an alkyl or cycloalkylgroup, and Rf represents (i) a halogen atom; (ii) fluoroalkyl; (iii) aper-halogenated aryl radical, or (iv) a radical selected fromR_(A)—CF₂—, R_(A)—CF₂—CF₂—, R_(A)—CF₂—CF(CF₃)—, CF₃—C(R_(A))F— and(CF₃)R_(A)—, with R_(A) selected from an alkyl, acyl, aryl, aralkyl,alkene or alkyne group, the cyclic hydrocarbons or the heterocycles, ora salt of a compound of formula (I).
 2. Compound according to claim 1,having the formula (Ia):

in which Z₁, Z₂, Z₃, Z₄ and Rf are as defined in claim
 1. 3. Compoundaccording to claim 2, in which Z₂ and Z₃ represent, independently ofeach other, a hydrogen atom, a group selected from the alkyls,cycloalkyls, aryls, and the electroattractive groups, wherein at leastone of the radicals Z₂ and Z₃ has an electroattractive effect withrespect to the electron density of the nitrogen atom to which they arebonded.
 4. Compound according to claim 1, having the formula (Ib):

in which Z₁, Z₄, Z₅ and Rf are as defined in claim
 1. 5. Compoundaccording to claim 1, having the formula (Ic):

in which Rf, Z₁, Hal and Z₄ are as defined in claim
 1. 6. Compoundaccording to claim 1, wherein Z₄ is a hydrogen atom.
 7. Compoundaccording to claim 1, wherein Rf is a perfluoroalkyl group or a poly- orper-halogenated aryl radical comprising at least one fluorine atom. 8.Compound according to claim 7, wherein the perfluoroalkyl group is thetrifluoromethyl radical.
 9. Compound according to claim 1, wherein Z₅ orat least one of the groups Z₂ and Z₃ represents an electroattractivegroup.
 10. Compound according to claim 9, wherein Z₅ or at least one ofthe groups Z₂ and Z₃ represents an electroattractive group selected froman acyl, an alkoxycarbonyl and an aralkyloxycarbonyl group.
 11. Compoundaccording to claim 10, wherein the electroattractive group is selectedfrom the acetyl, t-butoxycarbonyl and benzyloxycarbonyl groups. 12.Compound according to claim 9, wherein the group Z₂ or Z₃ that is notrepresent an electroattacrtive group represents a hydrogen atom. 13.Compound according to claim 1, wherein Z₁ represents a —OR^(a) or aR^(a) group as defined in claim
 1. 14. Compound according to claim 13,wherein R^(a) represents an alkyl group.
 15. Compound according to claim1, wherein the Hal group is a chlorine atom.
 16. Compound according toclaim 1, wherein Z₅ is a hydrogen atom.
 17. Compound according to claim1, wherein said compound is:S-[1-(N-acetylamino)-2,2,2-trifluoroethyl]-O-ethyl dithiocarbonate;O-ethyl and S-1-tert-butylamino-2,2,2-trifluoro-ethyl diester ofdithiocarbonic acid; O-ethyl and S-(1-hydroxy-2,2,2trifluoro-ethyl)ester of dithiocarbonic acid; O-ethyl andS-(1-acetyl-2,2,2-trifluoro-ethyl) ester of dithiocarbonic acid;1-ethoxythiocarbonylsulphanyl-2,2,2-trifluoro-ethyl ester of benzoicacid; O-ethyl and S-1-chloro-2,2,2-trifluoro-ethyl ester ofdithiocarbonic acid.
 18. Method for preparing a compound having theformula (Ib), in which Z₅ is different from H comprising: a. reacting acompound as defined in claim 1 wherein Z₅ is a hydrogen atom and acompound Z₅—Y, in which Z₅ is as defined in claim 1 and Y refers to aleaving group; and optionally b. recovering the product obtained. 19.Compound according to claim 9, wherein said each said electroattractivegroup is independently selected from the group consisting of acyl,aroyl, carboxyl, alkyloxycarbonyl, aryloxycarbonyl, aralkyloxycarbonyl,carbamoyl, alkylcarbamoyl, arylcarbamoyl, cyano-, sulphonyl,alkylsulphonyl, and arylsulphonyl groups.